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.

Effective field theory in the harmonic oscillator basis

DOE PAGES

Binder, S.; Ekström, Jan A.; Hagen, Gaute; ...

2016-04-25

In this paper, we develop interactions from chiral effective field theory (EFT) that are tailored to the harmonic oscillator basis. As a consequence, ultraviolet convergence with respect to the model space is implemented by construction and infrared convergence can be achieved by enlarging the model space for the kinetic energy. In oscillator EFT, matrix elements of EFTs formulated for continuous momenta are evaluated at the discrete momenta that stem from the diagonalization of the kinetic energy in the finite oscillator space. By fitting to realistic phase shifts and deuteron data we construct an effective interaction from chiral EFT at next-to-leadingmore » order. Finally, many-body coupled-cluster calculations of nuclei up to 132Sn converge fast for the ground-state energies and radii in feasible model spaces.« less

Analysis of general power counting rules in effective field theory

DOE PAGES

Gavela, Belen; Jenkins, Elizabeth E.; Manohar, Aneesh V.; ...

2016-09-02

We derive the general counting rules for a quantum effective field theory (EFT) in d dimensions. The rules are valid for strongly and weakly coupled theories, and they predict that all kinetic energy terms are canonically normalized. They determine the energy dependence of scattering cross sections in the range of validity of the EFT expansion. We show that the size of the cross sections is controlled by the Λ power counting of EFT, not by chiral counting, even for chiral perturbation theory (χPT). The relation between Λ and f is generalized to d dimensions. We show that the naive dimensionalmore » analysis 4π counting is related to ℏ counting. The EFT counting rules are applied to χPT, low-energy weak interactions, Standard Model EFT and the non-trivial case of Higgs EFT.« less

Bayesian parameter estimation for chiral effective field theory

NASA Astrophysics Data System (ADS)

Wesolowski, Sarah; Furnstahl, Richard; Phillips, Daniel; Klco, Natalie

2016-09-01

The low-energy constants (LECs) of a chiral effective field theory (EFT) interaction in the two-body sector are fit to observable data using a Bayesian parameter estimation framework. By using Bayesian prior probability distributions (pdfs), we quantify relevant physical expectations such as LEC naturalness and include them in the parameter estimation procedure. The final result is a posterior pdf for the LECs, which can be used to propagate uncertainty resulting from the fit to data to the final observable predictions. The posterior pdf also allows an empirical test of operator redundancy and other features of the potential. We compare results of our framework with other fitting procedures, interpreting the underlying assumptions in Bayesian probabilistic language. We also compare results from fitting all partial waves of the interaction simultaneously to cross section data compared to fitting to extracted phase shifts, appropriately accounting for correlations in the data. Supported in part by the NSF and DOE.

Chiral helimagnetic state in a Kondo lattice model with the Dzyaloshinskii-Moriya interaction

NASA Astrophysics Data System (ADS)

Okumura, Shun; Kato, Yasuyuki; Motome, Yukitoshi

2018-05-01

Monoaxial chiral magnets can form a noncollinear twisted spin structure called the chiral helimagnetic state. We study magnetic properties of such a chiral helimagnetic state, with emphasis on the effect of itinerant electrons. Modeling a monoaxial chiral helimagnet by a one-dimensional Kondo lattice model with the Dzyaloshinskii-Moriya interaction, we perform a variational calculation to elucidate the stable spin configuration in the ground state. We obtain a chiral helimagnetic state as a candidate for the ground state, whose helical pitch is modulated by the model parameters: the Kondo coupling, the Dzyaloshinski-Moriya interaction, and electron filling.

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

PubMed

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

2014-08-14

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

Nucleon form factors in dispersively improved chiral effective field theory: Scalar form factor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alarcon Soriano, Jose Manuel; Weiss, Christian

We propose a method for calculating the nucleon form factors (FFs) ofmore » $G$-parity-even operators by combining Chiral Effective Field Theory ($$\\chi$$EFT) and dispersion analysis. The FFs are expressed as dispersive integrals over the two-pion cut at $$t > 4 M_\\pi^2$$. The spectral functions are obtained from the elastic unitarity condition and expressed as products of the complex $$\\pi\\pi \\rightarrow N\\bar N$$ partial-wave amplitudes and the timelike pion FF. $$\\chi$$EFT is used to calculate the ratio of the partial-wave amplitudes and the pion FF, which is real and free of $$\\pi\\pi$$ rescattering in the $t$-channel ($N/D$ method). The rescattering effects are then incorporated by multiplying with the squared modulus of the empirical pion FF. The procedure results in a marked improvement compared to conventional $$\\chi$$EFT calculations of the spectral functions. We apply the method to the nucleon scalar FF and compute the scalar spectral function, the scalar radius, the $t$-dependent FF, and the Cheng-Dashen discrepancy. Higher-order chiral corrections are estimated through the $$\\pi N$$ low-energy constants. Results are in excellent agreement with dispersion-theoretical calculations. We elaborate several other interesting aspects of our method. The results show proper scaling behavior in the large-$$N_c$$ limit of QCD because the $$\\chi$$EFT includes $N$ and $$\\Delta$$ intermediate states. The squared modulus of the timelike pion FF required by our method can be extracted from Lattice QCD calculations of vacuum correlation functions of the operator at large Euclidean distances. Our method can be applied to the nucleon FFs of other operators of interest, such as the isovector-vector current, the energy-momentum tensor, and twist-2 QCD operators (moments of generalized parton distributions).« less

Nucleon form factors in dispersively improved chiral effective field theory: Scalar form factor

DOE PAGES

Alarcon Soriano, Jose Manuel; Weiss, Christian

2017-11-20

We propose a method for calculating the nucleon form factors (FFs) ofmore » $G$-parity-even operators by combining Chiral Effective Field Theory ($$\\chi$$EFT) and dispersion analysis. The FFs are expressed as dispersive integrals over the two-pion cut at $$t > 4 M_\\pi^2$$. The spectral functions are obtained from the elastic unitarity condition and expressed as products of the complex $$\\pi\\pi \\rightarrow N\\bar N$$ partial-wave amplitudes and the timelike pion FF. $$\\chi$$EFT is used to calculate the ratio of the partial-wave amplitudes and the pion FF, which is real and free of $$\\pi\\pi$$ rescattering in the $t$-channel ($N/D$ method). The rescattering effects are then incorporated by multiplying with the squared modulus of the empirical pion FF. The procedure results in a marked improvement compared to conventional $$\\chi$$EFT calculations of the spectral functions. We apply the method to the nucleon scalar FF and compute the scalar spectral function, the scalar radius, the $t$-dependent FF, and the Cheng-Dashen discrepancy. Higher-order chiral corrections are estimated through the $$\\pi N$$ low-energy constants. Results are in excellent agreement with dispersion-theoretical calculations. We elaborate several other interesting aspects of our method. The results show proper scaling behavior in the large-$$N_c$$ limit of QCD because the $$\\chi$$EFT includes $N$ and $$\\Delta$$ intermediate states. The squared modulus of the timelike pion FF required by our method can be extracted from Lattice QCD calculations of vacuum correlation functions of the operator at large Euclidean distances. Our method can be applied to the nucleon FFs of other operators of interest, such as the isovector-vector current, the energy-momentum tensor, and twist-2 QCD operators (moments of generalized parton distributions).« less

Interaction of chiral rafts in self-assembled colloidal membranes

NASA Astrophysics Data System (ADS)

Xie, Sheng; Hagan, Michael F.; Pelcovits, Robert A.

2016-03-01

Colloidal membranes are monolayer assemblies of rodlike particles that capture the long-wavelength properties of lipid bilayer membranes on the colloidal scale. Recent experiments on colloidal membranes formed by chiral rodlike viruses showed that introducing a second species of virus with different length and opposite chirality leads to the formation of rafts—micron-sized domains of one virus species floating in a background of the other viruses [Sharma et al., Nature (London) 513, 77 (2014), 10.1038/nature13694]. In this article we study the interaction of such rafts using liquid crystal elasticity theory. By numerically minimizing the director elastic free energy, we predict the tilt angle profile for both a single raft and two rafts in a background membrane, and the interaction between two rafts as a function of their separation. We find that the chiral penetration depth in the background membrane sets the scale for the range of the interaction. We compare our results with the experimental data and find good agreement for the strength and range of the interaction. Unlike the experiments, however, we do not observe a complete collapse of the data when rescaled by the tilt angle at the raft edge.

Cloning and characterization of EF-Tu and EF-Ts from Pseudomonas aeruginosa.

PubMed

Palmer, Stephanie O; Rangel, Edna Y; Montalvo, Alberto E; Tran, Alexis T; Ferguson, Kate C; Bullard, James M

2013-01-01

We have cloned genes encoding elongation factors EF-Tu and EF-Ts from Pseudomonas aeruginosa and expressed and purified the proteins to greater than 95% homogeneity. Sequence analysis indicated that P. aeruginosa EF-Tu and EF-Ts are 84% and 55% identical to E. coli counterparts, respectively. P. aeruginosa EF-Tu was active when assayed in GDP exchange assays. Kinetic parameters for the interaction of EF-Tu with GDP in the absence of EF-Ts were observed to be K M = 33 μM, k cat (obs) = 0.003 s(-1), and the specificity constant k cat (obs)/K M was 0.1 × 10(-3) s(-1) μM(-1). In the presence of EF-Ts, these values were shifted to K M = 2 μM, k cat (obs) = 0.005 s(-1), and the specificity constant k(cat)(obs)/K M was 2.5 × 10(-3) s(-1) μM(-1). The equilibrium dissociation constants governing the binding of EF-Tu to GDP (K GDP) were 30-75 nM and to GTP (K GTP) were 125-200 nM. EF-Ts stimulated the exchange of GDP by EF-Tu 10-fold. P. aeruginosa EF-Tu was active in forming a ternary complex with GTP and aminoacylated tRNA and was functional in poly(U)-dependent binding of Phe-tRNA(Phe) at the A-site of P. aeruginosa ribosomes. P. aeruginosa EF-Tu was active in poly(U)-programmed polyphenylalanine protein synthesis system composed of all P. aeruginosa components.

Properties of Nuclei up to A = 16 using Local Chiral Interactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lonardoni, Diego; Carlson, Joseph; Gandolfi, Stefano

Here, we report accurate quantum Monte Carlo calculations of nuclei up to A = 16 based on local chiral two- and three-nucleon interactions up to next-to-next-to-leading order. We examine the theoretical uncertainties associated with the chiral expansion and the cutoff in the theory, as well as the associated operator choices in the three-nucleon interactions. While in light nuclei the cutoff variation and systematic uncertainties are rather small, in 16O these can be significant for large coordinate-space cutoffs. Overall, we show that chiral interactions constructed to reproduce properties of very light systems and nucleon-nucleon scattering give an excellent description of bindingmore » energies, charge radii, and form factors for all these nuclei, including open-shell systems in A = 6 and 12.« less

Properties of Nuclei up to A = 16 using Local Chiral Interactions

DOE PAGES

Lonardoni, Diego; Carlson, Joseph; Gandolfi, Stefano; ...

2018-03-22

Here, we report accurate quantum Monte Carlo calculations of nuclei up to A = 16 based on local chiral two- and three-nucleon interactions up to next-to-next-to-leading order. We examine the theoretical uncertainties associated with the chiral expansion and the cutoff in the theory, as well as the associated operator choices in the three-nucleon interactions. While in light nuclei the cutoff variation and systematic uncertainties are rather small, in 16O these can be significant for large coordinate-space cutoffs. Overall, we show that chiral interactions constructed to reproduce properties of very light systems and nucleon-nucleon scattering give an excellent description of bindingmore » energies, charge radii, and form factors for all these nuclei, including open-shell systems in A = 6 and 12.« less

Chirality-induced spin polarization places symmetry constraints on biomolecular interactions.

PubMed

Kumar, Anup; Capua, Eyal; Kesharwani, Manoj K; Martin, Jan M L; Sitbon, Einat; Waldeck, David H; Naaman, Ron

2017-03-07

Noncovalent interactions between molecules are key for many biological processes. Necessarily, when molecules interact, the electronic charge in each of them is redistributed. Here, we show experimentally that, in chiral molecules, charge redistribution is accompanied by spin polarization. We describe how this spin polarization adds an enantioselective term to the forces, so that homochiral interaction energies differ from heterochiral ones. The spin polarization was measured by using a modified Hall effect device. An electric field that is applied along the molecules causes charge redistribution, and for chiral molecules, a Hall voltage is measured that indicates the spin polarization. Based on this observation, we conjecture that the spin polarization enforces symmetry constraints on the biorecognition process between two chiral molecules, and we describe how these constraints can lead to selectivity in the interaction between enantiomers based on their handedness. Model quantum chemistry calculations that rigorously enforce these constraints show that the interaction energy for methyl groups on homochiral molecules differs significantly from that found for heterochiral molecules at van der Waals contact and shorter (i.e., ∼0.5 kcal/mol at 0.26 nm).

$$\\chi$$EFT studies of few-nucleon systems: a status report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schiavilla, Rocco

2016-06-01

A status report onmore » $$\\chi$$EFT studies of few-nucleon electroweak structure and dynamics is provided, including electromagnetic elastic form factors of few-nucleon systems, the $pp$ weak fusion and muon weak captures on deuteron and $^3$He, and a number of parity-violating processes induced by hadronic weak interactions.« less

Strangeness S =-1 hyperon-nucleon interactions: Chiral effective field theory versus lattice QCD

NASA Astrophysics Data System (ADS)

Song, Jing; Li, Kai-Wen; Geng, Li-Sheng

2018-06-01

Hyperon-nucleon interactions serve as basic inputs to studies of hypernuclear physics and dense (neutron) stars. Unfortunately, a precise understanding of these important quantities has lagged far behind that of the nucleon-nucleon interaction due to lack of high-precision experimental data. Historically, hyperon-nucleon interactions are either formulated in quark models or meson exchange models. In recent years, lattice QCD simulations and chiral effective field theory approaches start to offer new insights from first principles. In the present work, we contrast the state-of-the-art lattice QCD simulations with the latest chiral hyperon-nucleon forces and show that the leading order relativistic chiral results can already describe the lattice QCD data reasonably well. Given the fact that the lattice QCD simulations are performed with pion masses ranging from the (almost) physical point to 700 MeV, such studies provide a useful check on both the chiral effective field theory approaches as well as lattice QCD simulations. Nevertheless more precise lattice QCD simulations are eagerly needed to refine our understanding of hyperon-nucleon interactions.

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

PubMed

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

2017-11-01

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

The Leuven Embedded Figures Test (L-EFT): measuring perception, intelligence or executive function?

PubMed Central

Van der Hallen, Ruth; Wagemans, Johan; de-Wit, Lee; Chamberlain, Rebecca

2018-01-01

Performance on the Embedded Figures Test (EFT) has been interpreted as a reflection of local/global perceptual style, weak central coherence and/or field independence, as well as a measure of intelligence and executive function. The variable ways in which EFT findings have been interpreted demonstrate that the construct validity of this measure is unclear. In order to address this lack of clarity, we investigated to what extent performance on a new Embedded Figures Test (L-EFT) correlated with measures of intelligence, executive functions and estimates of local/global perceptual styles. In addition, we compared L-EFT performance to the original group EFT to directly contrast both tasks. Taken together, our results indicate that performance on the L-EFT does not correlate strongly with estimates of local/global perceptual style, intelligence or executive functions. Additionally, the results show that performance on the L-EFT is similarly associated with memory span and fluid intelligence as the group EFT. These results suggest that the L-EFT does not reflect a general perceptual or cognitive style/ability. These results further emphasize that empirical data on the construct validity of a task do not always align with the face validity of a task. PMID:29607257

Uncertainty analysis of 208Pb neutron skin predictions with chiral interactions

DOE PAGES

Sammarruca, Francesca

2015-09-14

Here, we report predictions for the neutron skin in 208Pb using chiral two- and three-body interactions at increasing orders of chiral effective field theory and varying resolution scales. Closely related quantities, such as the slope of the symmetry energy, are also discussed. As a result, the sensitivity of the skin to just pure neutron matter pressure when going from order 2 to order 4 of chiral effective theory is singled out in a set of calculations that employ an empirical equation of state for symmetric nuclear matter.

Tritium β decay in chiral effective field theory

DOE PAGES

Baroni, A.; Girlanda, L.; Kievsky, A.; ...

2016-08-18

We evaluate the Fermi and Gamow-Teller (GT) matrix elements in tritiummore » $$\\beta$$-decay by including in the charge-changing weak current the corrections up to one loop recently derived in nuclear chiral effective field theory ($$\\chi$$ EFT). The trinucleon wave functions are obtained from hyperspherical-harmonics solutions of the Schroedinger equation with two- and three-nucleon potentials corresponding to either $$\\chi$$ EFT (the N3LO/N2LO combination) or meson-exchange phenomenology (the AV18/UIX combination). We find that contributions due to loop corrections in the axial current are, in relative terms, as large as (and in some cases, dominate) those from one-pion exchange, which nominally occur at lower order in the power counting. Furthermore, we also provide values for the low-energy constants multiplying the contact axial current and three-nucleon potential, required to reproduce the experimental GT matrix element and trinucleon binding energies in the N3LO/N2LO and AV18/UIX calculations.« less

Self-consistent Models of Strong Interaction with Chiral Symmetry

DOE R&D Accomplishments Database

Nambu, Y.; Pascual, P.

1963-04-01

Some simple models of (renormalizable) meson-nucleon interaction are examined in which the nucleon mass is entirely due to interaction and the chiral ( gamma {sub 5}) symmetry is "broken'' to become a hidden symmetry. It is found that such a scheme is possible provided that a vector meson is introduced as an elementary field. (auth)

Molecular description of the propagation of chirality from molecules to complex systems: different mechanisms controlled by hydrophobic interactions.

PubMed

Marinelli, Fabrizio; Sorrenti, Alessandro; Corvaglia, Valentina; Leone, Vanessa; Mancini, Giovanna

2012-11-12

In this work a combined theoretical and experimental approach was used to elucidate and describe at the molecular level the basic interactions that drive the transfer of the chiral information from chiral surfactant molecules to dye/surfactant assemblies. It was found that both hydrophobic interactions and relative concentrations strongly influence the chiroptical features of the heteroaggregates. In particular it was observed that, depending on the length of the surfactant hydrophobic chain, the chiral information is transferred to the dye by stabilizing an enantiomer either of a chiral conformer or of a chiral topological arrangement. These findings underline the role of hydrophobic interactions in the transfer of chirality and provide an example of the potential of in silico simulations for providing an accurate description of the process of chirality propagation. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

INTERACTION OF TWO FILAMENT CHANNELS OF DIFFERENT CHIRALITIES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Joshi, Navin Chandra; Magara, Tetsuya; Moon, Yong-Jae

2016-07-10

We present observations of the interactions between the two filament channels of different chiralities and associated dynamics that occurred during 2014 April 18–20. While two flux ropes of different helicity with parallel axial magnetic fields can only undergo a bounce interaction when they are brought together, the observations at first glance show that the heated plasma is moving from one filament channel to the other. The SDO /AIA 171 Å observations and the potential-field source-surface magnetic field extrapolation reveal the presence of a fan-spine magnetic configuration over the filament channels with a null point located above them. Three different eventsmore » of filament activations, partial eruptions, and associated filament channel interactions have been observed. The activation initiated in one filament channel seems to propagate along the neighboring filament channel. We believe that the activation and partial eruption of the filaments brings the field lines of flux ropes containing them closer to the null point and triggers the magnetic reconnection between them and the fan-spine magnetic configuration. As a result, the hot plasma moves along the outer spine line toward the remote point. Utilizing the present observations, for the first time we have discussed how two different-chirality filament channels can interact and show interrelation.« less

Enzyme-Inspired Chiral Secondary-Phosphine-Oxide Ligand with Dual Noncovalent Interactions for Asymmetric Hydrogenation.

PubMed

Chen, Caiyou; Zhang, Zhefan; Jin, Shicheng; Fan, Xiangru; Geng, Mingyu; Zhou, Yan; Wen, Songwei; Wang, Xinrui; Chung, Lung Wa; Dong, Xiu-Qin; Zhang, Xumu

2017-06-06

Inspired by the unique character of enzymes, we developed novel chiral SPO (secondary-phosphine-oxide) ligand (SPO-Wudaphos) which can enter into both ion pair and H-bond noncovalent interactions. The novel chiral SPO-Wudaphos exhibited excellent results in the asymmetric hydrogenation of α-methylene-γ-keto carboxylic acids, affording the chiral γ-keto acids with up to over 99 % ee. A series of control experiments and DFT calculations were conducted to illustrate the critical roles of both the ion pair and H-bond noncovalent interactions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of the kinetics of guanine nucleotide exchange on EF-Tu and EF-Ts: continuing uncertainties.

PubMed

Manchester, Keith L

2004-01-30

An analysis is made of the rate constants for the reactions involving the interactions of EF-Tu, EF-Ts, GDP, and GTP recently derived by Gromadski et al. [Biochemistry 41 (2002) 162]. Though their measured values appear to allow a reasonable rate of nucleotide exchange sufficient to support rates of protein synthesis in vivo, their data underestimate the thermodynamic barrier involved in nucleotide exchange and therefore cannot be considered definitive. A kinetic scheme consistent with the thermodynamic barrier can be achieved by modification of various rate constants, particularly of those involving the release of EF-Ts from EF-Tu.GTP.EF-Ts, but such constants are markedly different from what are experimentally observed. It thus remains impossible at present satisfactorily to model guanine nucleotide exchange on EF-Tu, catalysed by EF-Ts by a double displacement mechanism, with experimentally derived rate constants. Metabolic control analysis has been applied to determine the degree of flux control of the different steps in the pathway.

Peripheral transverse densities of the baryon octet from chiral effective field theory and dispersion analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alarcón, J. M.; Hiller Blin, A. N.; Vicente Vacas, M. J.

2017-05-08

The baryon electromagnetic form factors are expressed in terms of two-dimensional densities describing the distribution of charge and magnetization in transverse space at fixed light-front time. In this paper, we calculate the transverse densities of the spin-1/2 flavor-octet baryons at peripheral distances b=O(Mmore » $$-1\\atop{π}$$) using methods of relativistic chiral effective field theory (χ EFT) and dispersion analysis. The densities are represented as dispersive integrals over the imaginary parts of the form factors in the timelike region (spectral functions). The isovector spectral functions on the two-pion cut t > 4 M$$2\\atop{π}$$ are calculated using relativistic χEFT including octet and decuplet baryons. The χEFT calculations are extended into the ρ meson mass region using an N/D method that incorporates the pion electromagnetic form factor data. The isoscalar spectral functions are modeled by vector meson poles. We compute the peripheral charge and magnetization densities in the octet baryon states, estimate the uncertainties, and determine the quark flavor decomposition. Finally, the approach can be extended to baryon form factors of other operators and the moments of generalized parton distributions.« less

Formation of Coaxial Nanocables with Amplified Supramolecular Chirality through an Interaction between Carbon Nanotubes and a Chiral π-Gelator.

PubMed

Vedhanarayanan, Balaraman; Nair, Vishnu S; Nair, Vijayakumar C; Ajayaghosh, Ayyappanpillai

2016-08-22

In an attempt to gather experimental evidence for the influence of carbon allotropes on supramolecular chirality, we found that carbon nanotubes (CNTs) facilitate amplification of the molecular chirality of a π-gelator (MC-OPV) to supramolecular helicity at a concentration much lower than that required for intermolecular interaction. For example, at a concentration 1.8×10(-4)  m, MC-OPV did not exhibit a CD signal; however, the addition of 0-0.6 mg of SWNTs resulted in amplified chirality as evident from the CD spectrum. Surprisingly, AFM analysis revealed the formation of thick helical fibers with a width of more than 100 nm. High-resolution TEM analysis and solid-state UV/Vis/NIR spectroscopy revealed that the thick helical fibers were cylindrical cables composed of individually wrapped and coaxially aligned SWNTs. Such an impressive effect of CNTs on supramolecular chirality and cylindrical-cable formation has not been reported previously. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bayesian Methods for Effective Field Theories

NASA Astrophysics Data System (ADS)

Wesolowski, Sarah

Microscopic predictions of the properties of atomic nuclei have reached a high level of precision in the past decade. This progress mandates improved uncertainty quantification (UQ) for a robust comparison of experiment with theory. With the uncertainty from many-body methods under control, calculations are now sensitive to the input inter-nucleon interactions. These interactions include parameters that must be fit to experiment, inducing both uncertainty from the fit and from missing physics in the operator structure of the Hamiltonian. Furthermore, the implementation of the inter-nucleon interactions is not unique, which presents the additional problem of assessing results using different interactions. Effective field theories (EFTs) take advantage of a separation of high- and low-energy scales in the problem to form a power-counting scheme that allows the organization of terms in the Hamiltonian based on their expected contribution to observable predictions. This scheme gives a natural framework for quantification of uncertainty due to missing physics. The free parameters of the EFT, called the low-energy constants (LECs), must be fit to data, but in a properly constructed EFT these constants will be natural-sized, i.e., of order unity. The constraints provided by the EFT, namely the size of the systematic uncertainty from truncation of the theory and the natural size of the LECs, are assumed information even before a calculation is performed or a fit is done. Bayesian statistical methods provide a framework for treating uncertainties that naturally incorporates prior information as well as putting stochastic and systematic uncertainties on an equal footing. For EFT UQ Bayesian methods allow the relevant EFT properties to be incorporated quantitatively as prior probability distribution functions (pdfs). Following the logic of probability theory, observable quantities and underlying physical parameters such as the EFT breakdown scale may be expressed as pdfs that

Positron Interactions with Oriented Polymers and with Chiral Quartz Crystals

NASA Astrophysics Data System (ADS)

Wu, Fei

Positron annihilation in various materials has been applied to characterize microstructure for decades. In this work, PALS was used to study material nanostructure, with a focus on the size and density of free volume and hole relaxation properties in polycarbonate (PC) and polymethylmethacrylate (PMMA); fundamental studies of polarized positron interaction with chiral crystals were also studied. Free volume relaxation in PC and PMMA with different levels of simple shear orientation was studied by PALS. Effects of applied pressure on the free volume recovery were evaluated. Combining the bulk- and pressure-dependent PALS analyses, the removal of applied pressure led to free-volume relaxation in all samples studied. The alignment of the polymer chains and free-volume holes imposes molecular restrictions on the molecular mobility of both PC and PMMA in their glassy states. Results indicated that the relaxation of the free volume holes at temperatures below glass transition is mostly reversible. Longitudinally polarized positron particles were used to reveal asymmetric interactions in chiral quartz crystals. Experimental results showed a significant intensity difference in free positronium annihilation for left handed (LH) and right handed (RH) chiral quartz crystals. Doppler broadening energy spectra (DBES) of z-cut LH or RH quartz disks at different angles were also measured by an "S parameter" to probe the observed difference. It was found that obtained annihilation energy difference of DBES was in agreement with the result of positron annihilation in bulk chiral crystals. PALS was used to compare different orientations and confirm asymmetric interactions in natural versus synthetic quartz LH and RH crystals in z and non-z orientations. Significant lifetime and intensity differences in free positronium annihilation for LH and RH quartz crystals were observed. The trend was found to be same in the related crystallographic orientations of the LH or RH crystals; the

Λ N → NN EFT potentials and hypertriton non-mesonic weak decay

NASA Astrophysics Data System (ADS)

Pérez-Obiol, Axel; Entem, David R.; Nogga, Andreas

2018-05-01

The potential for the Λ N → NN weak transition, the main responsible for the non-mesonic weak decay of hypernuclei, has been developed within the framework of effective field theory (EFT) up to next-to-leading order (NLO). The leading order (LO) and NLO contributions have been calculated in both momentum and coordinate space, and have been organised into the different operators which mediate the N → NN transition. We compare the ranges of the one-meson and two-pion exchanges for each operator. The non-mesonic weak decay of the hypertriton has been computed within the plane-wave approximation using the LO weak potential and modern strong EFT NN potentials. Formally, two methods to calculate the final state interactions among the decay products are presented. We briefly comment on the calculation of the {}{{Λ }}{}3H{\\to }3 He+{π }- mesonic weak decay.

Molecular recognition in chiral smectic liquid crystals: the effect of core-core interactions and chirality transfer on polar order.

PubMed

Lemieux, Robert P

2007-12-01

This critical review focuses on the induction of polar order in smectic liquid crystal phases by dopants with axially chiral cores, and should be of interest to all practitioners of supramolecular chemistry. The variations in polarization power of these dopants with the core structure of the liquid crystal hosts is a manifestation of molecular recognition that reflects the nanosegregation of aromatic cores from paraffinic side-chains in smectic phases, and the collective effect of core-core interactions that enable the propagation of chiral perturbations.

RKKY interaction in a chirally coupled double quantum dot system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heine, A. W.; Tutuc, D.; Haug, R. J.

2013-12-04

The competition between the Kondo effect and the Ruderman-Kittel-Kasuya-Yoshida (RKKY) interaction is investigated in a double quantum dots system, coupled via a central open conducting region. A perpendicular magnetic field induces the formation of Landau Levels which in turn give rise to the so-called Kondo chessboard pattern in the transport through the quantum dots. The two quantum dots become therefore chirally coupled via the edge channels formed in the open conducting area. In regions where both quantum dots exhibit Kondo transport the presence of the RKKY exchange interaction is probed by an analysis of the temperature dependence. The thus obtainedmore » Kondo temperature of one dot shows an abrupt increase at the onset of Kondo transport in the other, independent of the magnetic field polarity, i.e. edge state chirality in the central region.« less

Future DUNE constraints on EFT

NASA Astrophysics Data System (ADS)

Falkowski, Adam; Grilli di Cortona, Giovanni; Tabrizi, Zahra

2018-04-01

In the near future, fundamental interactions at high-energy scales may be most efficiently studied via precision measurements at low energies. A universal language to assemble and interpret precision measurements is the so-called SMEFT, which is an effective field theory (EFT) where the Standard Model (SM) Lagrangian is extended by higher-dimensional operators. In this paper we investigate the possible impact of the DUNE neutrino experiment on constraining the SMEFT. The unprecedented neutrino flux offers an opportunity to greatly improve the current limits via precision measurements of the trident production and neutrino scattering off electrons and nuclei in the DUNE near detector. We quantify the DUNE sensitivity to dimension-6 operators in the SMEFT Lagrangian, and find that in some cases operators suppressed by an O(30) TeV scale can be probed. We also compare the DUNE reach to that of future experiments involving atomic parity violation and polarization asymmetry in electron scattering, which are sensitive to an overlapping set of SMEFT parameters.

Transverse Densities of Octet Baryons from Chiral Effective Field Theory

DOE PAGES

Alarcón, Jose Manuel; Hiller Blin, Astrid N.; Weiss, Christian

2017-03-24

Transverse densities describe the distribution of charge and current at fixed light-front time and provide a frame-independent spatial representation of hadrons as relativistic systems. In this paper, we calculate the transverse densities of the octet baryons at peripheral distances b=O(M π -1) in an approach that combines chiral effective field theory (χχEFT) and dispersion analysis. The densities are represented as dispersive integrals of the imaginary parts of the baryon electromagnetic form factors in the timelike region (spectral functions). The spectral functions on the two-pion cut at t>4Mmore » $$2\\atop{π}$$ are computed using relativistic χEFT with octet and decuplet baryons in the extended on-mass-shell renormalization scheme. The calculations are extended into the ρ-meson mass region using a dispersive method that incorporates the timelike pion form-factor data. The approach allows us to construct densities at distances b>1 fm with controlled uncertainties. Finally, our results provide insight into the peripheral structure of nucleons and hyperons and can be compared with empirical densities and lattice-QCD calculations.« less

Anagostic interactions in chiral separation. Polymorphism in a [Co(II)(L)] complex: Crystallographic and theoretical studies

NASA Astrophysics Data System (ADS)

Awwadi, Firas F.; Hodali, Hamdallah A.

2018-02-01

Syntheses and crystal structures of two polymorphs of the complex [Co(II)(L)], where H2L = 2,2'-[cis-1,2-diaminocyclohexanediylbis (nitrilo-methylidyne)]bis (5-dimethyl-amino]phenol, have been studied. The two polymorphs concomitantly crystallized by vapour diffusion of solvent. The first polymorph (I) crystallized as a racemate in the centrosymmetric tetragonal I41/a space group. The second polymorph (II) crystallized in the chiral orthorhombic space group P212121. The chiral conformers of symmetrical cis-1,2-disubstituted cyclohexane molecules cannot be resolved in the liquid or gas phases, due to the rapid ring inversion. In the present study, the two chiral conformers are present in crystals of polymorph I, whereas, only one chiral conformer is present in crystals of polymorph II. Crystal structure analysis indicated that the formation of two different polymorphs of [Co(II)(L)] complex can be rationalized based on Csbnd H⋯Co anagostic interactions. Density Functional Theory (DFT) calculations indicated that Csbnd H⋯Co interactions are due to HOMO-LUMO interactions.

Advanced Command Destruct System (ACDS) Enhanced Flight Termination System (EFTS)

NASA Technical Reports Server (NTRS)

Tow, David K.

2011-01-01

This presentation provides information on the development, integration, and operational usage of the Enhanced Flight Termination System (EFTS) at NASA Dryden Flight Research Center and Air Force Flight Test Center. The presentation will describe the efforts completed to certify the system and acquire approval for operational usage, the efforts to integrate the system into the NASA Dryden existing flight termination infrastructure, and the operational support of aircraft with EFTS at Edwards AFB.

Chiral effective-field theory of the nucleon spin structure

NASA Astrophysics Data System (ADS)

Pascalutsa, Vladimir

2017-01-01

I will review the recent chiral EFT calculations of the nucleon (spin) structure functions at low Q2, confronted with the Jefferson Lab measurements. The moments of the structure functions correspond with various polarizabilities, and I will explain why one of them - δLT - is especially interesting. I will also discuss how the spin structure functions at low Q enter in the atomic calculations of the hyperfine splittings and how they are impacting the ongoing experimental program at PSI (Switzerland) to measure the ground-state hyperfine splitting of muonic hydrogen. Partially supported by the Deutsche Forschungsgemeinschaft (DFG) through the Collaborative Research Center SFB 1044 [The Low-Energy Frontier of the Standard Model].

Observation of chiral phonons

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

Chiral liquid crystal colloids

NASA Astrophysics Data System (ADS)

Yuan, Ye; Martinez, Angel; Senyuk, Bohdan; Tasinkevych, Mykola; Smalyukh, Ivan I.

2018-01-01

Colloidal particles disturb the alignment of rod-like molecules of liquid crystals, giving rise to long-range interactions that minimize the free energy of distorted regions. Particle shape and topology are known to guide this self-assembly process. However, how chirality of colloidal inclusions affects these long-range interactions is unclear. Here we study the effects of distortions caused by chiral springs and helices on the colloidal self-organization in a nematic liquid crystal using laser tweezers, particle tracking and optical imaging. We show that chirality of colloidal particles interacts with the nematic elasticity to predefine chiral or racemic colloidal superstructures in nematic colloids. These findings are consistent with numerical modelling based on the minimization of Landau-de Gennes free energy. Our study uncovers the role of chirality in defining the mesoscopic order of liquid crystal colloids, suggesting that this feature may be a potential tool to modulate the global orientated self-organization of these systems.

On dark matter interactions with the Standard Model through an anomalous Z'

NASA Astrophysics Data System (ADS)

Ismail, Ahmed; Katz, Andrey; Racco, Davide

2017-10-01

We study electroweak scale Dark Matter (DM) whose interactions with baryonic matter are mediated by a heavy anomalous Z'. We emphasize that when the DM is a Majorana particle, its low-velocity annihilations are dominated by loop suppressed annihilations into the gauge bosons, rather than by p-wave or chirally suppressed annihilations into the SM fermions. Because the Z ' is anomalous, these kinds of DM models can be realized only as effective field theories (EFTs) with a well-defined cutoff, where heavy spectator fermions restore gauge invariance at high energies. We formulate these EFTs, estimate their cutoff and properly take into account the effect of the Chern-Simons terms one obtains after the spectator fermions are integrated out. We find that, while for light DM collider and direct detection experiments usually provide the strongest bounds, the bounds at higher masses are heavily dominated by indirect detection experiments, due to strong annihilation into W + W -, ZZ, Zγ and possibly into gg and γγ. We emphasize that these annihilation channels are generically significant because of the structure of the EFT, and therefore these models are prone to strong indirect detection constraints. Even though we focus on selected Z' models for illustrative purposes, our setup is completely generic and can be used for analyzing the predictions of any anomalous Z'-mediated DM model with arbitrary charges.

Chiral Three-Nucleon Interactions in Light Nuclei, Neutron-α Scattering, and Neutron Matter

DOE PAGES

Lynn, J. E.; Tews, I.; Carlson, Joseph Allen; ...

2016-02-09

Here we present quantum Monte Carlo calculations of light nuclei, neutron- scattering, and neutron matter using local two- and three-nucleon (3N) interactions derived from chiral e effective fi eld theory up to next-to-next-to-leading order (N 2LO). The two undetermined 3N low-energy couplings are fi t to the 4He binding energy and, for the first time, to the spin-orbit splitting in the neutron- P-wave phase shifts. Furthermore, we investigate different choices of local 3N-operator structures and find that chiral interactions at N 2LO are able to simultaneously reproduce the properties of A = 3; 4; 5 systems and of neutron matter,more » in contrast to commonly used phenomenological 3N interactions.« less

Chiral Three-Nucleon Interactions in Light Nuclei, Neutron-α Scattering, and Neutron Matter

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lynn, J. E.; Tews, I.; Carlson, Joseph Allen

Here we present quantum Monte Carlo calculations of light nuclei, neutron- scattering, and neutron matter using local two- and three-nucleon (3N) interactions derived from chiral e effective fi eld theory up to next-to-next-to-leading order (N 2LO). The two undetermined 3N low-energy couplings are fi t to the 4He binding energy and, for the first time, to the spin-orbit splitting in the neutron- P-wave phase shifts. Furthermore, we investigate different choices of local 3N-operator structures and find that chiral interactions at N 2LO are able to simultaneously reproduce the properties of A = 3; 4; 5 systems and of neutron matter,more » in contrast to commonly used phenomenological 3N interactions.« less

Auxiliary field diffusion Monte Carlo calculations of light and medium-mass nuclei with local chiral interactions

NASA Astrophysics Data System (ADS)

Lonardoni, D.; Gandolfi, S.; Lynn, J. E.; Petrie, C.; Carlson, J.; Schmidt, K. E.; Schwenk, A.

2018-04-01

Quantum Monte Carlo methods have recently been employed to study properties of nuclei and infinite matter using local chiral effective-field-theory interactions. In this work, we present a detailed description of the auxiliary field diffusion Monte Carlo algorithm for nuclei in combination with local chiral two- and three-nucleon interactions up to next-to-next-to-leading order. We show results for the binding energy, charge radius, charge form factor, and Coulomb sum rule in nuclei with 3 ≤A ≤16 . Particular attention is devoted to the effect of different operator structures in the three-body force for different cutoffs. The outcomes suggest that local chiral interactions fit to few-body observables give a very good description of the ground-state properties of nuclei up to 16O, with the exception of one fit for the softer cutoff which predicts overbinding in larger nuclei.

Active chiral fluids.

PubMed

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

2012-09-01

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

Chiral Responsive Liquid Quantum Dots.

PubMed

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

2017-08-01

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

Auxiliary field diffusion Monte Carlo calculations of light and medium-mass nuclei with local chiral interactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lonardoni, D.; Gandolfi, S.; Lynn, J. E.

Quantum Monte Carlo methods have recently been employed to study properties of nuclei and infinite matter using local chiral effective-field-theory interactions. In this paper, we present a detailed description of the auxiliary field diffusion Monte Carlo algorithm for nuclei in combination with local chiral two- and three-nucleon interactions up to next-to-next-to-leading order. We show results for the binding energy, charge radius, charge form factor, and Coulomb sum rule in nuclei withmore » $$3{\\le}A{\\le}16$$. Particular attention is devoted to the effect of different operator structures in the three-body force for different cutoffs. Finally, the outcomes suggest that local chiral interactions fit to few-body observables give a very good description of the ground-state properties of nuclei up to $$^{16}\\mathrm{O}$$, with the exception of one fit for the softer cutoff which predicts overbinding in larger nuclei.« less

Auxiliary field diffusion Monte Carlo calculations of light and medium-mass nuclei with local chiral interactions

DOE PAGES

Lonardoni, D.; Gandolfi, S.; Lynn, J. E.; ...

2018-04-24

Quantum Monte Carlo methods have recently been employed to study properties of nuclei and infinite matter using local chiral effective-field-theory interactions. In this paper, we present a detailed description of the auxiliary field diffusion Monte Carlo algorithm for nuclei in combination with local chiral two- and three-nucleon interactions up to next-to-next-to-leading order. We show results for the binding energy, charge radius, charge form factor, and Coulomb sum rule in nuclei withmore » $$3{\\le}A{\\le}16$$. Particular attention is devoted to the effect of different operator structures in the three-body force for different cutoffs. Finally, the outcomes suggest that local chiral interactions fit to few-body observables give a very good description of the ground-state properties of nuclei up to $$^{16}\\mathrm{O}$$, with the exception of one fit for the softer cutoff which predicts overbinding in larger nuclei.« less

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

PubMed

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

2017-05-31

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

Quark structure of chiral solitons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dmitri Diakonov

2004-05-01

There is a prejudice that the chiral soliton model of baryons is something orthogonal to the good old constituent quark models. In fact, it is the opposite: the spontaneous chiral symmetry breaking in strong interactions explains the appearance of massive constituent quarks of small size thus justifying the constituent quark models, in the first place. Chiral symmetry ensures that constituent quarks interact very strongly with the pseudoscalar fields. The ''chiral soliton'' is another word for the chiral field binding constituent quarks. We show how the old SU(6) quark wave functions follow from the ''soliton'', however, with computable relativistic corrections andmore » additional quark-antiquark pairs. We also find the 5-quark wave function of the exotic baryon Theta+.« less

Observation of chiral phonons.

PubMed

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

2018-02-02

Chirality reveals symmetry breaking of the fundamental interaction of elementary particles. In condensed matter, for example, the chirality of electrons governs many unconventional transport phenomena such as the quantum Hall effect. Here we show that phonons can exhibit intrinsic chirality in monolayer tungsten diselenide. The broken inversion symmetry of the lattice lifts the degeneracy of clockwise and counterclockwise phonon modes at the corners of the Brillouin zone. We identified the phonons by the intervalley transfer of holes through hole-phonon interactions during the indirect infrared absorption, and we confirmed their chirality by the infrared circular dichroism arising from pseudoangular momentum conservation. The chiral phonons are important for electron-phonon coupling in solids, phonon-driven topological states, and energy-efficient information processing. Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

Chirality dependent interaction of ammonia with carbon nanotubes

NASA Astrophysics Data System (ADS)

Talukdar, Keka; Shantappa, Anil

2018-04-01

For the specific structure and extraordinary properties, carbon nanotubes (CNTs) have many applications in diversified fields. The interaction of CNTs with ammonia is a very interesting matter to study as it is related to the application of CNTs as ammonia sensor. Here the interaction of single walled zigzag, armchair and chiral carbon nanotubes is studied in respect of the change in energies before and after binding with ammonia by molecular dynamics simulation. Their deformation after simulation is modeled. The change of thermal conductivity of the CNTs is also found by simulation. The potential energy before and after absorption of ammonia gives useful information of the system. Thermal conductivities of the ammonia bound CNTs are changed considerably. It is observed that the potential energy and thermal conductivity both are changing for the interaction with ammonia and hence they are sensitive to ammonia binding.

Quantum Monte Carlo calculations of light nuclei with local chiral two- and three-nucleon interactions

DOE PAGES

Lynn, J. E.; Tews, I.; Carlson, J.; ...

2017-11-30

Local chiral effective field theory interactions have recently been developed and used in the context of quantum Monte Carlo few- and many-body methods for nuclear physics. In this paper, we go over detailed features of local chiral nucleon-nucleon interactions and examine their effect on properties of the deuteron, paying special attention to the perturbativeness of the expansion. We then turn to three-nucleon interactions, focusing on operator ambiguities and their interplay with regulator effects. We then discuss the nuclear Green's function Monte Carlo method, going over both wave-function correlations and approximations for the two- and three-body propagators. Finally, following this, wemore » present a range of results on light nuclei: Binding energies and distribution functions are contrasted and compared, starting from several different microscopic interactions.« less

Cosmic chirality both true and false.

PubMed

Barron, Laurence D

2012-12-01

The discrete symmetries of parity P, time reversal T, and charge conjugation C may be used to characterize the properties of chiral systems. It is well known that parity violation infiltrates into ordinary matter via an interaction between the nucleons and electrons, mediated by the Z(0) particle, that lifts the degeneracy of the mirror-image enantiomers of a chiral molecule. Being odd under P but even under T, this P-violating interaction exhibits true chirality and so may induce absolute enantioselection under all circumstances. It has been suggested that CP violation may also infiltrate into ordinary matter via a P-odd, T-odd interaction mediated by the (as yet undetected) axion. This CP-violating interaction exhibits false chirality and so may induce absolute enantioselection in processes far from equilibrium. Both true and false cosmic chirality should be considered together as possible sources of homochirality in the molecules of life. Copyright © 2012 Wiley Periodicals, Inc.

SRAG Measurements Performed During the Orion EFT-1 Mission

NASA Technical Reports Server (NTRS)

Gaza, Ramona

2015-01-01

The Exploration Flight Test 1 (EFT-1) was the first flight of the Orion Multi-Purpose Crew Vehicle (MPCV). The flight was launched on December 5, 2014, by a Delta IV Heavy rocket and lasted 4.5 hours. The EFT-1 trajectory involved one low altitude orbit and one high altitude orbit with an apogee of almost 6000 km. As a result of this particular flight profile, the Orion MPCV passed through intense regions of trapped protons and electron belts. In support of the radiation measurements aboard the EFT-1, the Space Radiation Analysis Group (SRAG) provided a Battery-operated Independent Radiation Detector (BIRD) based on Timepix radiation monitoring technology similar to that employed by the ISS Radiation Environmental Monitors (REM). In addition, SRAG provided a suite of optically and thermally stimulated luminescence detectors, with 2 Radiation Area Monitor (RAM) units collocated with the BIRD instrument for comparison purposes, and 6 RAM units distributed at different shielding configurations within the Orion MPCV. A summary of the EFT-1 Radiation Area Monitors (RAM) mission dose results obtained from measurements performed in the Space Radiation Dosimetry Laboratory at the NASA Johnson Space Center will be presented. Each RAM included LiF:Mg,Ti (TLD-100), (6)LiF:Mg,Ti (TLD-600), (7)LiF:Mg,Ti (TLD-700), Al2O3:C (Luxel trademark), and CaF2:Tm (TLD-300). The RAM mission dose values will be compared with the BIRD instrument total mission dose. In addition, a similar comparison will be shown for the ISS environment by comparing the ISS RAM data with data from the six Timepix-based REM units deployed on ISS as part of the NASA REM Technology Demonstration.

Molecular self assembly and chiral recognition of copper octacyanophthalocyanine on Au(111): Interplay of intermolecular and molecule-substrate interactions.

NASA Astrophysics Data System (ADS)

Sk, Rejaul; Dhara, Barun; Miller, Joel; Deshpande, Aparna

Submolecular resolution scanning tunneling microscopy (STM) of copper octacyanophthalocyanine, CuPc(CN)8, at 77 K demonstrates that these achiral molecules form a two dimensional (2D) tetramer-based self-assembly upon evaporation onto an atomically flat Au(111) substrate. They assemble in two different structurally chiral configurations upon adsorption on Au(111). Scanning tunneling spectroscopy (STS),acquired at 77 K, unveils the HOMO and LUMO energy levels of this self-assembly. Voltage dependent STM images show that each molecule in both the structurally chiral configurations individually becomes chiral by breaking the mirror symmetry due to the enhanced intermolecular dipolar coupling interaction at the LUMO energy while the individual molecules remain achiral at the HOMO energy and within the HOMO-LUMO gap. At the LUMO energy, the handedness of the each chiral molecule is decided by the direction of the dipolar coupling interaction in the tetramer unit cell. This preference for LUMO energy indicates that this chirality is purely electronic in nature and it manifests on top of the organizational chirality that is present in the self-assembly independent of the orbital energy. Supported by IISER Pune and DAE-BRNS, India (Project No. 2011/20/37C/17/BRNS).

Nucleon form factors in dispersively improved chiral effective field theory. II. Electromagnetic form factors

NASA Astrophysics Data System (ADS)

Alarcón, J. M.; Weiss, C.

2018-05-01

We study the nucleon electromagnetic form factors (EM FFs) using a recently developed method combining chiral effective field theory (χ EFT ) and dispersion analysis. The spectral functions on the two-pion cut at t >4 Mπ2 are constructed using the elastic unitarity relation and an N /D representation. χ EFT is used to calculate the real functions J±1(t ) =f±1(t ) /Fπ(t ) (ratios of the complex π π →N N ¯ partial-wave amplitudes and the timelike pion FF), which are free of π π rescattering. Rescattering effects are included through the empirical timelike pion FF | Fπ(t) | 2 . The method allows us to compute the isovector EM spectral functions up to t ˜1 GeV2 with controlled accuracy (leading order, next-to-leading order, and partial next-to-next-to-leading order). With the spectral functions we calculate the isovector nucleon EM FFs and their derivatives at t =0 (EM radii, moments) using subtracted dispersion relations. We predict the values of higher FF derivatives, which are not affected by higher-order chiral corrections and are obtained almost parameter-free in our approach, and explain their collective behavior. We estimate the individual proton and neutron FFs by adding an empirical parametrization of the isoscalar sector. Excellent agreement with the present low-Q2 FF data is achieved up to ˜0.5 GeV2 for GE, and up to ˜0.2 GeV2 for GM. Our results can be used to guide the analysis of low-Q2 elastic scattering data and the extraction of the proton charge radius.

EFT-1 Crew Module on Display at KSC Visitor Complex

NASA Image and Video Library

2017-04-12

The Orion crew module from Exploration Flight Test 1 (EFT-1) is on display at nearby NASA Kennedy Space Center Visitor Complex in Florida. The crew module is part of the NASA Now exhibit in the IMAX Theater. Also in view is a scale model of NASA's Space Launch System rocket and Orion spacecraft on the mobile launcher. The Orion EFT-1 spacecraft launched atop a United Launch Alliance Delta IV rocket Dec. 5, 2014, from Space Launch Complex 37 at Cape Canaveral Air Force Station. The spacecraft built for humans traveled 3,604 miles above Earth and splashed down about 4.5 hours later in the Pacific Ocean.

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...

The effects of EF-Ts and bismuth on EF-Tu in Helicobacter pylori: implications for an elegant timing for the introduction of EF-Ts in the elongation and EF-Tu as a potential drug target.

PubMed

Wang, Dongxian; Luo, Benping; Shan, Weiran; Hao, Mingcong; Sun, Xuesong; Ge, Ruiguang

2013-06-01

Helicobacter pylori is a common human pathogen responsible for various gastric diseases. Bismuth can effectively inhibit the growth of this bacterium and is commonly recommended for the treatment of the related diseases. Translation elongation factors EF-Tu and EF-Ts are two important components of the protein translation system. EF-Ts has inhibitory effects on the GTPase activity of EF-Tu and enhances GDP release, a hint that careful timing for the introduction of EF-Ts in the elongation should be accomplished to prevent the complete inhibition of the elongation process. Bismuth inhibits the chaperone activity of EF-Tu, and has opposite effects on the elongation activity: inhibitory effects on the intrinsic GTPase activity and stimulation of GDP release. The present work deepens our understanding of the bacterial elongation process as mediated by EF-Tu and EF-Ts and extends our knowledge about the inhibitory effects of bismuth-based drugs against Helicobacter pylori.

Chirality in molecular collision dynamics

NASA Astrophysics Data System (ADS)

Lombardi, Andrea; Palazzetti, Federico

2018-02-01

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

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

PubMed

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

2016-02-24

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

Photoexcitation circular dichroism in chiral molecules

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

Theory of interaction-induced renormalization of Drude weight and plasmon frequency in chiral multilayer graphene

NASA Astrophysics Data System (ADS)

Li, Xiao; Tse, Wang-Kong

2017-02-01

We develop a theory for the optical conductivity of doped ABC-stacked multilayer graphene including the effects of electron-electron interactions. Applying the quantum kinetic formalism, we formulate a set of pseudospin Bloch equations that govern the dynamics of the nonequilibrium density matrix driven by an external ac electric field under the influence of Coulomb interactions. These equations reveal a dynamical mechanism that couples the Drude and interband responses arising from the chirality of pseudospin textures in multilayer graphene systems. We demonstrate that this results in an interaction-induced enhancement of the Drude weight and plasmon frequency strongly dependent on the pseudospin winding number. Using bilayer graphene as an example, we also study the influence of higher-energy bands and find that they contribute considerable renormalization effects not captured by a low-energy two-band description. We argue that this enhancement of Drude weight and plasmon frequency occurs generally in materials characterized by electronic chirality.

Light-Nuclei Spectra from Chiral Dynamics

NASA Astrophysics Data System (ADS)

Piarulli, M.; Baroni, A.; Girlanda, L.; Kievsky, A.; Lovato, A.; Lusk, Ewing; Marcucci, L. E.; Pieper, Steven C.; Schiavilla, R.; Viviani, M.; Wiringa, R. B.

2018-02-01

In recent years local chiral interactions have been derived and implemented in quantum Monte Carlo methods in order to test to what extent the chiral effective field theory framework impacts our knowledge of few- and many-body systems. In this Letter, we present Green's function Monte Carlo calculations of light nuclei based on the family of local two-body interactions presented by our group in a previous paper in conjunction with chiral three-body interactions fitted to bound- and scattering-state observables in the three-nucleon sector. These interactions include Δ intermediate states in their two-pion-exchange components. We obtain predictions for the energy levels and level ordering of nuclei in the mass range A =4 - 12 , accurate to ≤2 % of the binding energy, in very satisfactory agreement with experimental data.

Effect of molecular structure of tartrates on chiral recognition of tartrate-boric acid complex chiral selectors in chiral microemulsion electrokinetic chromatography.

PubMed

Hu, Shao-Qiang; Chen, Yong-Lei; Zhu, Hua-Dong; Shi, Hai-Jun; Yan, Na; Chen, Xing-Guo

2010-08-20

Eight l-tartrates and a d-tartrate with different alcohol moieties were used as chiral oils to prepare chiral microemulsions, which were utilized in conjunction with borate buffer to separate the enantiomers of beta-blockers or structurally related compounds by the chiral microemulsion electrokinetic chromatography (MEEKC) method. Among them, six were found to have a relatively good chiral separation performance and their chiral recognition effect in terms of both enantioselectivity and resolution increases linearly with the number of carbon atoms in the alkyl group of alcohol moiety. The tartrates containing alkyl groups of different structures but the same number of carbon atoms, i.e. one of straight chain and one of branched chain, provide similar enantioseparations. The trend was elucidated according to the changes in the difference of the steric matching between the molecules of two enantiomers and chiral selector. Furthermore, it was demonstrated for the first time that a water insoluble solid compound, di-i-butyl l-tartrate (mp. 73.5 degrees C), can be used as an oil to prepare a stable microemulsion to be used in the chiral MEEKC successfully. And a critical effect of the microemulsion for chiral separation, which has never been reported before, was found in this experiment, namely providing a hydrophobic environment to strengthen the interactions between the chiral selector and enantiomers. Copyright 2010 Elsevier B.V. All rights reserved.

Chiral permselectivity in surface-modified nanoporous opal films.

PubMed

Cichelli, Julie; Zharov, Ilya

2006-06-28

Nanoporous 7 mum thin opal films comprising 35 layers of 200 nm diameter SiO2 spheres were assembled on Pt electrodes and modified with chiral selector moieties on the silica surface. Diffusion of chiral redox species through the opals was studied by cyclic voltammetry. The chiral opal films demonstrate high selectivity for transport of one enantiomer over the other. This chiral permselectivity is attributed to the surface-facilitated transport utilizing noncovalent interactions between the chiral permeant molecules and surface-bound chiral selectors.

Light-Nuclei Spectra from Chiral Dynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Piarulli, M.; Baroni, A.; Girlanda, L.

In recent years local chiral interactions have been derived and implemented in quantum Monte Carlo methods in order to test to what extent the chiral effective field theory framework impacts our knowledge of few- and many-body systems. Here in this Letter, we present Green’s function Monte Carlo calculations of light nuclei based on the family of local two-body interactions presented by our group in a previous paper in conjunction with chiral three-body interactions fitted to bound- and scattering-state observables in the three-nucleon sector. These interactions include Δ intermediate states in their two-pion-exchange components. We obtain predictions for the energy levelsmore » and level ordering of nuclei in the mass range A=4–12, accurate to ≤2% of the binding energy, in very satisfactory agreement with experimental data.« less

Light-Nuclei Spectra from Chiral Dynamics

DOE PAGES

Piarulli, M.; Baroni, A.; Girlanda, L.; ...

2018-02-01

In recent years local chiral interactions have been derived and implemented in quantum Monte Carlo methods in order to test to what extent the chiral effective field theory framework impacts our knowledge of few- and many-body systems. Here in this Letter, we present Green’s function Monte Carlo calculations of light nuclei based on the family of local two-body interactions presented by our group in a previous paper in conjunction with chiral three-body interactions fitted to bound- and scattering-state observables in the three-nucleon sector. These interactions include Δ intermediate states in their two-pion-exchange components. We obtain predictions for the energy levelsmore » and level ordering of nuclei in the mass range A=4–12, accurate to ≤2% of the binding energy, in very satisfactory agreement with experimental data.« less

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

NASA Astrophysics Data System (ADS)

Kehr, Nermin Seda; Jose, Joachim

2017-12-01

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

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.

Chiral magnetic effect in the presence of electroweak interactions as a quasiclassical phenomenon

NASA Astrophysics Data System (ADS)

Dvornikov, Maxim; Semikoz, Victor B.

2018-03-01

We elaborate the quasiclassical approach to obtain the modified chiral magnetic effect (CME) in the case when the massless charged fermions interact with electromagnetic fields and the background matter by the electroweak forces. The derivation of the anomalous current along the external magnetic field involves the study of the energy density evolution of chiral particles in parallel electric and magnetic fields. We consider both the particle acceleration by the external electric field and the contribution of the Adler anomaly. The condition of the validity of this method for the derivation of the CME is formulated. We obtain the expression for the electric current along the external magnetic field, which appears to coincide with our previous results based on the purely quantum approach. Our results are compared with the findings of other authors.

FATE AND EFFECTS OF THE ENANTIOMERS OF CHIRAL ENVIRONMENTAL POLLUTANTS

EPA Science Inventory

Enantiomers, the mirror image isomers of chiral compounds, are known to be selective in their interaction with other chiral molecules, including enzymes and other biochemicals. This holds true for pesticides, about 25% of which are chiral molecules, and other chiral environmental...

Chiral nanoparticles in singular light fields

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

Similarity-transformed chiral NN + 3N interactions for the ab initio description of 12C and 16O.

PubMed

Roth, Robert; Langhammer, Joachim; Calci, Angelo; Binder, Sven; Navrátil, Petr

2011-08-12

We present first ab initio no-core shell model (NCSM) calculations using similarity renormalization group (SRG) transformed chiral two-nucleon (NN) plus three-nucleon (3N) interactions for nuclei throughout the p-shell, particularly (12)C and (16)O. By introducing an adaptive importance truncation for the NCSM model space and an efficient JT-coupling scheme for the 3N matrix elements, we are able to surpass previous NCSM studies including 3N interactions. We present ground and excited states in (12)C and (16)O for model spaces up to N(max) = 12 including full 3N interactions. We analyze the contributions of induced and initial 3N interactions and probe induced 4N terms through the sensitivity of the energies on the SRG flow parameter. Unlike for light p-shell nuclei, SRG-induced 4N contributions originating from the long-range two-pion terms of the chiral 3N interaction are sizable in (12)C and (16)O.

Statistical uncertainties of a chiral interaction at next-to-next-to leading order

DOE PAGES

Ekström, A.; Carlsson, B. D.; Wendt, K. A.; ...

2015-02-05

In this paper, we have quantified the statistical uncertainties of the low-energy coupling-constants (LECs) of an optimized nucleon–nucleon interaction from chiral effective field theory at next-to-next-to-leading order. Finally, in addition, we have propagated the impact of the uncertainties of the LECs to two-nucleon scattering phase shifts, effective range parameters, and deuteron observables.

Orion Exploration Flight Test-1 (EFT-1) Absolute Navigation Performance

NASA Technical Reports Server (NTRS)

Zanetti, Renato

2015-01-01

The Orion vehicle, being design to take men back to the Moon and beyond, successfully completed its first flight test, EFT-1 (Exploration Flight Test-1), on December 5th, 2014. The main objective of the test was to demonstrate the capability of re-enter into the Earth's atmosphere and safely splash-down into the pacific ocean. This un-crewed mission completes two orbits around Earth, the second of which is highly elliptical with an apogee of approximately 5908 km, higher than any vehicle designed for humans has been since the Apollo program. The trajectory was designed in order to test a high-energy re-entry similar to those crews will undergo during lunar missions. The mission overview is shown in Figure 1. The objective of this paper is to document the performance of the absolute navigation system during EFT-1 and to present its design.

Deep-Subwavelength Resolving and Manipulating of Hidden Chirality in Achiral Nanostructures.

PubMed

Zu, Shuai; Han, Tianyang; Jiang, Meiling; Lin, Feng; Zhu, Xing; Fang, Zheyu

2018-04-24

The chiral state of light plays a vital role in light-matter interactions and the consequent revolution of nanophotonic devices and advanced modern chiroptics. As the light-matter interaction goes into the nano- and quantum world, numerous chiroptical technologies and quantum devices require precise knowledge of chiral electromagnetic modes and chiral radiative local density of states (LDOS) distributions in detail, which directly determine the chiral light-matter interaction for applications such as chiral light detection and emission. With classical optical techniques failing to directly measure the chiral radiative LDOS, deep-subwavelength imaging and control of circular polarization (CP) light associated phenomena are introduced into the agenda. Here, we simultaneously reveal the hidden chiral electromagnetic mode and acquire its chiral radiative LDOS distribution of a single symmetric nanostructure at the deep-subwavelength scale by using CP-resolved cathodoluminescence (CL) microscopy. The chirality of the symmetric nanostructure under normally incident light excitation, resulting from the interference between the symmetric and antisymmetric modes of the V-shaped nanoantenna, is hidden in the near field with a giant chiral distribution (∼99%) at the arm-ends, which enables the circularly polarized CL emission from the radiative LDOS hot-spot and the following active helicity control at the deep-subwavelength scale. The proposed V-shaped nanostructure as a functional unit is further applied to the helicity-dependent binary encoding and the two-dimensional display applications. The proposed physical principle and experimental configuration can promote the future chiral characterization and manipulation at the deep-subwavelength scale and provide direct guidelines for the optimization of chiral light-matter interactions for future quantum studies.

Chiral nanoparticles in singular light fields

PubMed Central

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

2017-01-01

The studying of how twisted light interacts with chiral matter on the nanoscale is paramount for tackling the challenging task of optomechanical separation of nanoparticle enantiomers, whose solution can revolutionize the entire pharmaceutical industry. Here we calculate optical forces and torques exerted on chiral nanoparticles by Laguerre–Gaussian beams carrying a topological charge. We show that regardless of the beam polarization, the nanoparticles are exposed to both chiral and achiral forces with nonzero reactive and dissipative components. Longitudinally polarized beams are found to produce chirality densities that can be 109 times higher than those of transversely polarized beams and that are comparable to the chirality densities of beams polarized circularly. Our results and analytical expressions prove useful in designing new strategies for mechanical separation of chiral nanoobjects with the help of highly focussed beams. PMID:28378842

Selection of Amino Acid Chirality via Neutrino Interactions with 14N in Crossed Electric and Magnetic Fields

PubMed Central

Boyd, Richard N.; Kajino, Toshitaka; Onaka, Takashi

2018-01-01

Abstract Previous work has suggested that the chirality of the amino acids could be established in the magnetic field of a nascent neutron star from a core-collapse supernova or massive collapsar. The magnetic field would orient the 14N nuclei, and the alignment of its nuclear spin with respect to those of the electron antineutrinos emitted from the collapsing star would determine the probability of destruction of the 14N nuclei by interactions with the antineutrinos. Subsequent work estimated the bulk polarization of the 14N nuclei in large rotating meteoroids in such an environment. The present work adds a crucial piece of this model by describing the details by which the selective 14N nuclear destruction would produce molecular chiral selectivity. The effects of the neutrino-induced interactions on the 14N nuclei bound in amino acids polarized in strong magnetic fields are studied. It is shown that electric fields in the reference frame of the nuclei modify the magnetic field at the nucleus, creating nuclear magnetizations that are asymmetric in chirality. The antineutrino cross sections depend on this magnetization, creating a selective destructive effect. The environmental conditions and sites in which such a selection mechanism could occur are discussed. Selective destruction of D-enantiomers results in enantiomeric excesses which may be sufficient to drive subsequent autocatalysis necessary to produce the few-percent enantiomeric excesses found in meteorites and subsequent homochirality. Molecular quantum chemical calculations were performed for alanine, and the chirality-dependent effects studied were included. A preference for left-handed molecules was found, and enantiomeric excesses as high as 0.02% were estimated for molecules in the electromagnetic conditions expected from a core-collapse supernova. Key Words: Amino acids—Supernovae—Antineutrinos—Enantiomeric excess—Chirality. Astrobiology 18, 190–206. PMID:29160728

Orion Exploration Flight Test-l (EFT -1) Absolute Navigation Design

NASA Technical Reports Server (NTRS)

Sud, Jastesh; Gay, Robert; Holt, Greg; Zanetti, Renato

2014-01-01

Scheduled to launch in September 2014 atop a Delta IV Heavy from the Kennedy Space Center, the Orion Multi-Purpose-Crew-Vehicle (MPCV's) maiden flight dubbed "Exploration Flight Test -1" (EFT-1) intends to stress the system by placing the uncrewed vehicle on a high-energy parabolic trajectory replicating conditions similar to those that would be experienced when returning from an asteroid or a lunar mission. Unique challenges associated with designing the navigation system for EFT-1 are presented in the narrative with an emphasis on how redundancy and robustness influenced the architecture. Two Inertial Measurement Units (IMUs), one GPS receiver and three barometric altimeters (BALTs) comprise the navigation sensor suite. The sensor data is multiplexed using conventional integration techniques and the state estimate is refined by the GPS pseudorange and deltarange measurements in an Extended Kalman Filter (EKF) that employs the UDUT decomposition approach. The design is substantiated by simulation results to show the expected performance.

Onset of η-nuclear binding in a pionless EFT approach

NASA Astrophysics Data System (ADS)

Barnea, N.; Bazak, B.; Friedman, E.; Gal, A.

2017-08-01

ηNNN and ηNNNN bound states are explored in stochastic variational method (SVM) calculations within a pionless effective field theory (EFT) approach at leading order. The theoretical input consists of regulated NN and NNN contact terms, and a regulated energy dependent ηN contact term derived from coupled-channel models of the N* (1535) nucleon resonance. A self consistency procedure is applied to deal with the energy dependence of the ηN subthreshold input, resulting in a weak dependence of the calculated η-nuclear binding energies on the EFT regulator. It is found, in terms of the ηN scattering length aηN, that the onset of binding η 3He requires a minimal value of ReaηN close to 1 fm, yielding then a few MeV η binding in η 4He. The onset of binding η 4He requires a lower value of ReaηN, but exceeding 0.7 fm.

Chiral topological insulator of magnons

NASA Astrophysics Data System (ADS)

Li, Bo; Kovalev, Alexey A.

2018-05-01

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

The falsification of Chiral Nuclear Forces

NASA Astrophysics Data System (ADS)

Ruiz Arriola, E.; Amaro, J. E.; Navarro Perez, R.

2017-03-01

Predictive power in theoretical nuclear physics has been a major concern in the study of nuclear structure and reactions. The Effective Field Theory (EFT) based on chiral expansions provides a model independent hierarchy for many body forces at long distances but their predictive power may be undermined by the regularization scheme dependence induced by the counterterms and encoding the short distances dynamics which seem to dominate the uncertainties. We analyze several examples including zero energy NN scattering or perturbative counterterm-free peripheral scattering where one would expect these methods to work best and unveil relevant systematic discrepancies when a fair comparison to the Granada-2013 NN-database and partial wave analysis (PWA) is undertaken. Work supported by Spanish Ministerio de Economia y Competitividad and European FEDER funds (grant FIS2014-59386-P), the Agencia de Innovacion y Desarrollo de Andalucia (grant No. FQM225), the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract No. DE-AC52-07NA27344, U.S. Department of Energy, Office of Science, Office of Nuclear Physics under Award No. DE-SC0008511 (NUCLEI SciDAC Collaboration)

Emergence of Chiral Phases in Active Torque Dipole Systems

NASA Astrophysics Data System (ADS)

Fialho, Ana; Tjhung, Elsen; Cates, Michael; Marenduzzo, Davide

The common description of active particles as active force dipoles fails to take into account that active processes in biological systems often exhibit chiral asymmetries, generating active chiral processes and torque dipoles. Examples of such systems include cytoskeleton filaments which interact with motor proteins and beating cilia and flagella. In particular, the generation of active torques by the actomyosin cytoskeleton has been linked to the break of chiral symmetry at a cellular level. This phenomenon could constitute the primary determinant for the break of left-right symmetry in many living organisms, e.g. the position of the human heart within the human body. In order to account for the effects of chirality, we consider active torque dipoles which generate a chiral active stress. We characterize quasi-1D and 2D systems of torque dipoles, using a combination of linear stability analysis and numerical simulations (Lattice Boltzmann). Our results show that activity drives a spontaneous breaking of chiral symmetry, leading to the self-assembly of a chiral phase, in the absence of any thermodynamic interactions favoring cholesteric ordering. At high values of activity, we also observe labyrinthine patterns where the activity-induced chiral ordering is highly frustrated.

Coordinative Alignment of Chiral Molecules to Control over the Chirality Transfer in Spontaneous Resolution and Asymmetric Catalysis.

PubMed

Xia, Zhengqiang; Jing, Xu; He, Cheng; Wang, Xiaoge; Duan, Chunying

2017-11-13

The production and availability of enantiomerically pure compounds that spurred the development of chiral technologies and materials are very important to the fine chemicals and pharmaceutical industries. By coordinative alignment of enantiopure guests in the metal‒organic frameworks, we reported an approach to control over the chirality of homochiral crystallization and asymmetric transformation. Synthesized by achiral triphenylamine derivatives, the chirality of silver frameworks was determined by the encapsulated enantiopure azomethine ylides, from which clear interaction patterns were observed to explore the chiral induction principles. With the changing of addition sequence of substrates, the enantioselectivity of asymmetric cycloaddition was controlled to verify the determinant on the chirality of the bulky MOF materials. The economical chirality amplification that merges a series of complicated self-inductions, bulk homochiral crystallization and enantioselective catalysis opens new avenues for enantiopure chemical synthesis and provides a promising path for the directional design and development of homochiral materials.

Nuclear astrophysics and electron beams

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schwenk, A.

Electron beams provide important probes and constraints for nuclear astrophysics. This is especially exciting at energies within the regime of chiral effective field theory (EFT), which provides a systematic expansion for nuclear forces and electroweak operators based on quantum chromodynamics. This talk discusses some recent highlights and future directions based on chiral EFT, including nuclear structure and reactions for astrophysics, the neutron skin and constraints for the properties of neutron-rich matter in neutron stars and core-collapse supernovae, and the dark matter response of nuclei.

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

PubMed

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

2018-03-16

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

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

Influence of Chirality in Ordered Block Copolymer Phases

NASA Astrophysics Data System (ADS)

Prasad, Ishan; Grason, Gregory

2015-03-01

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

Nonperturbative NN scattering in {sup 3}S{sub 1}–{sup 3}D{sub 1} channels of EFT(⁄π)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Ji-Feng, E-mail: jfyang@phy.ecnu.edu.cn

2013-12-15

The closed-form T matrices in the {sup 3}S{sub 1}–{sup 3}D{sub 1} channels of EFT(⁄π) for NN scattering with the potentials truncated at order O(Q{sup 4}) are presented with the nonperturbative divergences parametrized in a general manner. The stringent constraints imposed by the closed form of the T matrices are exploited in the underlying theory perspective and turned into virtues in the implementation of subtractions and the manifestation of power counting rules in nonperturbative regimes, leading us to the concept of EFT scenario. A number of scenarios of the EFT description of NN scattering are compared with PSA data in termsmore » of effective range expansion and {sup 3}S{sub 1} phase shifts, showing that it is favorable to proceed in a scenario with conventional EFT couplings and sophisticated renormalization in order to have large NN scattering lengths. The informative utilities of fine tuning are demonstrated in several examples and naturally interpreted in the underlying theory perspective. In addition, some of the approaches adopted in the recent literature are also addressed in the light of EFT scenario. -- Highlights: •Closed-form unitary T matrices for NN scattering are obtained in EFT(⁄π). •Nonperturbative properties inherent in such closed-form T matrices are explored. •Nonperturbative renormalization is implemented through exploiting these properties. •Unconventional power counting of couplings is shown to be less favored by PSA data. •The ideas about nonperturbative renormalization here might have wider applications.« less

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

PubMed Central

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

2017-01-01

Noncovalently introducing stereogenic information is a promising approach to embed chirality in achiral molecular systems. However, the interplay of the noncovalently introduced chirality with the intrinsic chirality of molecules or molecular aggregations has rarely been addressed. We report a competitive chiral expression of the noncovalent interaction–mediated chirality induction and the intrinsic stereogenic center–controlled chirality induction in a two-dimensional (2D) molecular assembly at the liquid/solid interface. Two enantiomorphous honeycomb networks are formed by the coassembly of an achiral 5-(benzyloxy)isophthalic acid (BIC) derivative and 1-octanol at the liquid/solid interface. The preferential formation of the globally homochiral assembly can be achieved either by using the chiral analog of 1-octanol, (S)-6-methyl-1-octanol, as a chiral coadsorber to induce chirality to the BIC assembly via noncovalent hydrogen bonding or by covalently linking a chiral center in the side chain of BIC. Both the chiral coadsorber and the intrinsically chiral BIC derivative can act as a chiral seeds to induce a preferred handedness in the assembly of the achiral BIC derivatives. Furthermore, the noncovalent interaction–mediated chirality induction can restrain or even overrule the manifestation of the intrinsic chirality of the BIC molecule and dominate the handedness of the 2D molecular coassembly. This study provides insight into the interplay of intrinsically chiral centers and external chiral coadsorbers in the chiral induction, transfer, and amplification processes of 2D molecular assembly. PMID:29119137

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...

Chiral effective theory of dark matter direct detection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bishara, Fady; Brod, Joachim; Grinstein, Benjamin

2017-02-01

We present the effective field theory for dark matter interactions with the visible sector that is valid at scales of O(1 GeV). Starting with an effective theory describing the interactions of fermionic and scalar dark matter with quarks, gluons and photons via higher dimension operators that would arise from dimension-five and dimension-six operators above electroweak scale, we perform a nonperturbative matching onto a heavy baryon chiral perturbation theory that describes dark matter interactions with light mesons and nucleons. This is then used to obtain the coefficients of the nuclear response functions using a chiral effective theory description of nuclear forces.more » Our results consistently keep the leading contributions in chiral counting for each of the initial Wilson coefficients.« less

Toroidal Interaction and Propeller Chirality of Hexaarylbenzenes. Dynamic Domino Inversion Revealed by Combined Experimental and Theoretical Circular Dichroism Studies.

PubMed

Kosaka, Tomoyo; Inoue, Yoshihisa; Mori, Tadashi

2016-03-03

Hexaarylbenzenes (HABs) have greatly attracted much attention due to their unique propeller-shaped structure and potential application in materials science, such as liquid crystals, molecular capsules/rotors, redox materials, nonlinear optical materials, as well as molecular wires. Less attention has however been paid to their propeller chirality. By introducing small point-chiral group(s) at the periphery of HABs, propeller chirality was effectively induced, provoking strong Cotton effects in the circular dichroism (CD) spectrum. Temperature and solvent polarity manipulate the dynamics of propeller inversion in solution. As such, whizzing toroids become more substantial in polar solvents and at an elevated temperature, where radial aromatic rings (propeller blades) prefer orthogonal alignment against the central benzene ring (C6 core), maximizing toroidal interactions.

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

PubMed

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

2016-11-14

It is a challenging issue to achieve propeller chirality for triarylboranes owing to the low transition barrier between the P and M forms of the boron center. Herein, we report a new strategy to achieve propeller chirality of triarylboranes. It was found that the chirality relay from axially chiral 1,1'-binaphthyl to propeller chirality of the trivalent boron center can be realized when a Me 2 N and a Mes 2 B group (Mes=mesityl) are introduced at the 2,2'-positions of the 1,1'-binaphthyl skeleton (BN-BNaph) owing to the strong π-π interaction between the Me 2 N-bonded naphthyl ring and the phenyl ring of one adjacent Mes group, which not only exerts great steric hindrance on the rotation of the two Mes groups but also gives unequal stability to the two configurations of the boron center for a given configuration of the binaphthyl moiety. The stereostructures of the boron center were fully characterized through 1 H NMR spectroscopy, X-ray crystal analyses, and theoretical calculations. Detailed comparisons with the analog BN-Ph-BNaph, in which the Mes 2 B group is separated from 1,1'-binaphthyl by a para-phenylene spacer, confirmed the essential role of π-π interaction for the successful chirality relay in BN-BNaph. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chiral Gold Nanoclusters: Atomic Level Origins of Chirality.

PubMed

Zeng, Chenjie; Jin, Rongchao

2017-08-04

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

Asymmetric Michael Addition Mediated by Chiral Ionic Liquids.

PubMed

Suzuki, Yumiko

2018-06-01

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

Constraints on neutron star radii based on chiral effective field theory interactions.

PubMed

Hebeler, K; Lattimer, J M; Pethick, C J; Schwenk, A

2010-10-15

We show that microscopic calculations based on chiral effective field theory interactions constrain the properties of neutron-rich matter below nuclear densities to a much higher degree than is reflected in commonly used equations of state. Combined with observed neutron star masses, our results lead to a radius R=9.7-13.9  km for a 1.4M⊙ star, where the theoretical range is due, in about equal amounts, to uncertainties in many-body forces and to the extrapolation to high densities.

Leading order relativistic hyperon-nucleon interactions in chiral effective field theory

NASA Astrophysics Data System (ADS)

Li, Kai-Wen; Ren, Xiu-Lei; Geng, Li-Sheng; Long, Bing-Wei

2018-01-01

We apply a recently proposed covariant power counting in nucleon-nucleon interactions to study strangeness S=-1 {{\\varLambda }}N-{{\\varSigma }}N interactions in chiral effective field theory. At leading order, Lorentz invariance introduces 12 low energy constants, in contrast to the heavy baryon approach, where only five appear. The Kadyshevsky equation is adopted to resum the potential in order to account for the non-perturbative nature of hyperon-nucleon interactions. A fit to the 36 hyperon-nucleon scattering data points yields {χ }2≃ 16, which is comparable with the sophisticated phenomenological models and the next-to-leading order heavy baryon approach. However, one cannot achieve a simultaneous description of the nucleon-nucleon phase shifts and strangeness S=-1 hyperon-nucleon scattering data at leading order. Supported by the National Natural Science Foundation of China (11375024, 11522539, 11375120), the China Postdoctoral Science Foundation (2016M600845, 2017T100008) and the Fundamental Research Funds for the Central Universities

Cooperative expression of atomic chirality in inorganic nanostructures.

PubMed

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

2017-02-02

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

Cooperative expression of atomic chirality in inorganic nanostructures

PubMed Central

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

2017-01-01

Cooperative chirality phenomena extensively exist in biomolecular and organic systems via intra- and inter-molecular interactions, but study of inorganic materials has been lacking. Here we report, experimentally and theoretically, cooperative chirality in colloidal cinnabar mercury sulfide nanocrystals that originates from chirality interplay between the crystallographic lattice and geometric morphology at different length scales. A two-step synthetic scheme is developed to allow control of critical parameters of these two types of handedness, resulting in different chiral interplays expressed as observables through materials engineering. Furthermore, we adopt an electromagnetic model with the finite element method to elucidate cooperative chirality in inorganic systems, showing excellent agreement with experimental results. Our study enables an emerging class of nanostructures with tailored cooperative chirality that is vital for fundamental understanding of nanoscale chirality as well as technology applications based on new chiroptical building blocks. PMID:28148957

Fluorescence Turn-on Enantioselective Recognition of both Chiral Acidic Compounds and α-Amino Acids by a Chiral Tetraphenylethylene Macrocycle Amine.

PubMed

Feng, Hai-Tao; Zhang, Xing; Zheng, Yan-Song

2015-08-21

New chiral tetraphenylethylene (TPE) macrocycles bearing optically pure amine groups were synthesized and found to have a discriminating ability between the two enantiomers of not only chiral acidic compounds but also α-amino acids by enantioselective aggregation and aggregation-induced emission (AIE) effects. NMR spectra, including 2D-NOESY, disclosed that the host-guest interaction of the macrocycle receptor played a key role in addition to the acid-base interactions.

Centre vortex removal restores chiral symmetry

NASA Astrophysics Data System (ADS)

Trewartha, Daniel; Kamleh, Waseem; Leinweber, Derek B.

2017-12-01

The influence of centre vortices on dynamical chiral symmetry breaking is investigated through the light hadron spectrum on the lattice. Recent studies of the quark propagator and other quantities have provided evidence that centre vortices are the fundamental objects underpinning dynamical chiral symmetry breaking in {SU}(3) gauge theory. For the first time, we use the chiral overlap fermion action to study the low-lying hadron spectrum on lattice ensembles consisting of Monte Carlo, vortex-removed, and vortex-projected gauge fields. We find that gauge field configurations consisting solely of smoothed centre vortices are capable of reproducing all the salient features of the hadron spectrum, including dynamical chiral symmetry breaking. The hadron spectrum on vortex-removed fields shows clear signals of chiral symmetry restoration at light values of the bare quark mass, while at heavy masses the spectrum is consistent with a theory of weakly interacting constituent quarks.

Fluorescent Phthalocyanine Assembly Distinguishes Chiral Isomers of Different Types of Amino Acids and Sugars.

PubMed

Jiang, Yuying; Liu, Chenxi; Wang, Xiqian; Wang, Tianyu; Jiang, Jianzhuang

2017-07-25

The functions of some natural supramolecular architectures, such as ribosomes, are dependent on the recognition of different types of chiral biomolecules. However, the recognition of different types of chiral molecules (multiobject chiral recognition), such as amino acids and sugars, by independent and identically artificial supramolecular assembly, was rarely achieved. In this article, simple amphiphilic achiral phthalocyanine was found to form supramolecular chiral assemblies with charged water-soluble polymers upon host-guest interactions at the air/water interface. Among these systems, one identical phthalocyanine/poly(l-lysine) assembly not only can distinguish enantiomers of different amino acids but also can recognize several epimers of monose. The chiral recognitions were achieved by comparing either the steady-state fluorescence intensity or fluorescence quenching rate of phthalocyanine/poly(l-lysine) assemblies, before and after interaction with different small chiral molecules. It was demonstrated that the interactions between poly(l-lysine) and different small chiral molecules could change the aggregation of phthalocyanines. And the sensitivity of fluorescence and the excellent multiobject chiral recognition properties of the phthalocyanine/poly(l-lysine) assembly are dependent on the subtle molecular packing mode and the cooperation of different noncovalent interactions.

Chirality and the angular momentum of light

PubMed Central

Götte, Jörg B.; Barnett, Stephen M.; Yao, Alison M.

2017-01-01

Chirality is exhibited by objects that cannot be rotated into their mirror images. It is far from obvious that this has anything to do with the angular momentum of light, which owes its existence to rotational symmetries. There is nevertheless a subtle connection between chirality and the angular momentum of light. We demonstrate this connection and, in particular, its significance in the context of chiral light–matter interactions. This article is part of the themed issue ‘Optical orbital angular momentum’. PMID:28069764

Laminar and Turbulent Dynamos in Chiral Magnetohydrodynamics. I. Theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rogachevskii, Igor; Kleeorin, Nathan; Ruchayskiy, Oleg

2017-09-10

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

Chirality detection of enantiomers using twisted optical metamaterials

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

Chirality detection of enantiomers using twisted optical metamaterials

PubMed Central

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

2017-01-01

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

Asymmetric Michael Addition Mediated by Chiral Ionic Liquids

PubMed Central

Suzuki, Yumiko

2018-01-01

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

Centre vortex removal restores chiral symmetry

DOE PAGES

Trewartha, Daniel; Kamleh, Waseem; Leinweber, Derek B.

2017-11-15

The influence of centre vortices on dynamical chiral symmetry breaking is investigated through the light hadron spectrum on the lattice. Recent studies of the quark propagator and other quantities have provided evidence that centre vortices are the fundamental objects underpinning dynamical chiral symmetry breaking in SU(3) gauge theory. For the first time, we use the chiral overlap fermion action to study the low-lying hadron spectrum on lattice ensembles consisting of Monte Carlo, vortex-removed, and vortex-projected gauge fields. We find that gauge field configurations consisting solely of smoothed centre vortices are capable of reproducing all the salient features of the hadronmore » spectrum, including dynamical chiral symmetry breaking. In conclusion, the hadron spectrum on vortex-removed fields shows clear signals of chiral symmetry restoration at light values of the bare quark mass, while at heavy masses the spectrum is consistent with a theory of weakly-interacting constituent quarks.« less

Chiral Separations

NASA Astrophysics Data System (ADS)

Stalcup, A. M.

2010-07-01

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

Drag suppression in anomalous chiral media

DOE PAGES

Sadofyev, Andrey V.; Yin, Yi

2016-06-01

We study a heavy impurity moving longitudinal with the direction of an external magnetic field in an anomalous chiral medium. Such system would carry a non-dissipative current of chiral magnetic effect associated with the anomaly. We show, by generalizing Landau's criterion for super fluidity, that the "anomalous component" which gives rise to the anomalous transport will not contribute to the drag experienced by an impurity. We argue on a very general basis that those systems with a strong magnetic field would exhibit an interesting transport phenomenon$-$the motion of the heavy impurity is frictionless, in analogy to the case of amore » super fluid. Finally, we demonstrate and confirm our general results with two complementary examples: weakly coupled chiral fermion gases and strongly interacting chiral liquids.« less

Orion EFT-1 Cavity Heating Tile Experiments and Environment Reconstruction

NASA Technical Reports Server (NTRS)

Salazar, Giovanni; Amar, Adam; Oliver, Brandon; Hyatt, Andrew; Rezin, Marc

2016-01-01

Developing aerothermodynamic environments for deep cavities, such as those produced by micrometeoroids and orbital debris impacts, poses a great challenge for engineers. In order to assess existing cavity heating models, two one-inch diameter cavities were flown on the Orion Multi-Purpose Crew Vehicle during Exploration Flight Test 1 (EFT1). These cavities were manufactured with depths of 1.0 in and 1.4 in, and they were both instrumented. Instrumentation included surface thermocouples upstream, downstream and within the cavities, and additional thermocouples at the TPS-structure interface. This paper will present the data obtained, and comparisons with computational predictions will be shown. Additionally, the development of a 3D material thermal model will be described, which will be used to account for the three-dimensionality of the problem when interpreting the data. Furthermore, using a multi-dimensional inverse heat conduction approach, a reconstruction of a time- and space-dependent flight heating distribution during EFT1 will be presented. Additional discussions will focus on instrumentation challenges and calibration techniques specific to these experiments. The analysis shown will highlight the accuracies and/or deficiencies of current computational techniques to model cavity flows during hypersonic re-entry.

EFT (Emotional Freedom Techniques) and Resiliency in Veterans at Risk for PTSD: A Randomized Controlled Trial.

PubMed

Church, Dawson; Sparks, Terry; Clond, Morgan

2016-01-01

Prior research indicates elevated but subclinical posttraumatic stress disorder (PTSD) symptoms as a risk factor for a later diagnosis of PTSD. This study examined the progression of symptoms in 21 subclinical veterans. Participants were randomized into a treatment as usual (TAU) wait-list group and an experimental group, which received TAU plus six sessions of clinical emotional freedom techniques (EFT). Symptoms were assessed using the PCL-M (Posttraumatic Checklist-Military) on which a score of 35 or higher indicates increased risk for PTSD. The mean pretreatment score of participants was 39 ± 8.7, with no significant difference between groups. No change was found in the TAU group during the wait period. Afterward, the TAU group received an identical clinical EFT protocol. Posttreatment groups were combined for analysis. Scores declined to a mean of 25 (-64%, P < .0001). Participants maintained their gains, with mean three-month and six-month follow-up PCL-M scores of 27 (P < .0001). Similar reductions were noted in the depth and breadth of psychological conditions such as anxiety. A Cohen's d = 1.99 indicates a large treatment effect. Reductions in traumatic brain injury symptoms (P = .045) and insomnia (P = .004) were also noted. Symptom improvements were similar to those assessed in studies of PTSD-positive veterans. EFT may thus be protective against an increase in symptoms and a later PTSD diagnosis. As a simple and quickly learned self-help method, EFT may be a clinically useful element of a resiliency program for veterans and active-duty warriors. Copyright © 2016 Elsevier Inc. All rights reserved.

Phenomenology of anomalous chiral transports in heavy-ion collisions

NASA Astrophysics Data System (ADS)

Huang, Xu-Guang

2018-01-01

High-energy Heavy-ion collisions can generate extremely hot quark-gluon matter and also extremely strong magnetic fields and fluid vorticity. Once coupled to chiral anomaly, the magnetic fields and fluid vorticity can induce a variety of novel transport phenomena, including the chiral magnetic effect, chiral vortical effect, etc. Some of them require the environmental violation of parity and thus provide a means to test the possible parity violation in hot strongly interacting matter. We will discuss the underlying mechanism and implications of these anomalous chiral transports in heavy-ion collisions.

Delta Mariner arrival with EFT-1 Booster

NASA Image and Video Library

2014-03-03

CAPE CANAVERAL, Fla. – The United Launch Alliance barge Delta Mariner enters Port Canaveral in Florida. The barge is carrying two of the booster stages for the Delta IV Heavy rocket slated for Orion's Exploration Flight Test-1, or EFT-1. Orion is the exploration spacecraft designed to carry astronauts to destinations not yet explored by humans. It will have emergency abort capability, sustain the crew during space travel and provide safe re-entry from deep-space return velocities. The first unpiloted test flight of Orion is scheduled to launch in September 2014 atop a Delta IV Heavy rocket and in 2017 on NASA’s Space Launch System

Orion Exploration Flight Test 1 (EFT-1) Best Estimated Trajectory Development

NASA Technical Reports Server (NTRS)

Holt, Greg N.; Brown, Aaron

2016-01-01

The Orion Exploration Flight Test 1 (EFT-1) mission successfully flew on Dec 5, 2014 atop a Delta IV Heavy launch vehicle. The goal of Orions maiden flight was to stress the system by placing an uncrewed vehicle on a high-energy trajectory replicating conditions similar to those that would be experienced when returning from an asteroid or a lunar mission. The Orion navigation team combined all trajectory data from the mission into a Best Estimated Trajectory (BET) product. There were significant challenges in data reconstruction and many lessons were learned for future missions. The team used an estimation filter incorporating radar tracking, onboard sensors (Global Positioning System and Inertial Measurement Unit), and day-of-flight weather balloons to evaluate the true trajectory flown by Orion. Data was published for the entire Orion EFT-1 flight, plus objects jettisoned during entry such as the Forward Bay Cover. The BET customers include approximately 20 disciplines within Orion who will use the information for evaluating vehicle performance and influencing future design decisions.

Chiral Graphene Quantum Dots

DOE PAGES

Suzuki, Nozomu; Wang, Yichun; Elvati, Paolo; ...

2016-01-15

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

[Influence of mobile phase composition on chiral separation of organic selenium racemates].

PubMed

Han, Xiao-qian; Qi, Bang-feng; Dun, Hui-juan; Zhu, Xin-yi; Na, Peng-jun; Jiang, Sheng-xiang; Chen, Li-ren

2002-05-01

The chiral separation of some chiral compounds with similar structure on the cellulose tris (3,5-dimethylphenylcarbamate) chiral stationary phase prepared by us was obtained. Ternary mobile phases influencing chiral recognition were investigated. A mode of interaction between the structural character of samples and chiral stationary phase is discussed. The results indicated that the retention and chiral separation of the analytes had a bigger change with minute addition of alcohols or acetonitrile as modifier in n-hexane/2-propanol (80/20, volume ratio) binary mobile phase.

New mathematic model for predicting chiral separation using molecular docking: mechanism of chiral recognition of triadimenol analogues.

PubMed

Zhang, Guoqing; Sun, Qingyan; Hou, Ying; Hong, Zhanying; Zhang, Jun; Zhao, Liang; Zhang, Hai; Chai, Yifeng

2009-07-01

The purpose of this paper was to study the enantioseparation mechanism of triadimenol compounds by carboxymethylated (CM)-beta-CD mediated CE. All the enantiomers were separated under the same experimental conditions to study the chiral recognition mechanism using a 30 mM sodium dihydrogen phosphate buffer at pH 2.2 adjusted by phosphoric acid. The inclusion courses between CM-beta-CD and enantiomers were investigated by the means of molecular docking technique. It was found that there were at least three points (one hydrophobic bond and two hydrogen bonds) involved in the interaction of each enantiomer with the chiral selectors. A new mathematic model has been built up based on the results of molecular mechanics calculations, which could analyze the relationship between the resolution of enantioseparation and the interaction energy in the docking area. Comparing the results of the separation by CE, the established mathematic model demonstrated good capability to predict chiral separation of triadimenol enantiomers using CM-beta-CD mediated CE.

Self-assembled cyclodextrin-modified gold nanoparticles on silica beads as stationary phase for chiral liquid chromatography and hydrophilic interaction chromatography.

PubMed

Li, Yuanyuan; Wei, Manman; Chen, Tong; Zhu, Nan; Ma, Yulong

2016-11-01

A facile strategy based on self-assembly of Au nanoparticles (AuNPs) (60±10nm in size) on the surfaces of amino-functionalized porous silica spheres under mild conditions was proposed. The resulting material possessed a core-shell structure in which AuNPs were the shell and silica spheres were the core. Then, thiolated-β-cyclodextrin (SH-β-CD) was covalently attached onto the AuNPs as chiral selector for the enantioseparation. The resultant packing material was evaluated by high-performance liquid chromatography (HPLC). The separations of nine pairs of enantiomers were achieved by using the new chiral stationary phase (CSP) in the reversed-phase liquid chromatography (RPLC) mode, respectively. The results showed the new CSP have more sufficient interaction with the analytes due to the existence of AuNPs on silica surfaces, resulting in faster mass transfer rate, compared with β-CD modified silica column. The result shed light on potential usage of chemical modified NPs as chiral selector for enantioseparation based on HPLC. In addition, the new phase was also used in hydrophilic interaction liquid chromatography (HILIC) to separate polar compounds and highly hydrophilic compounds. Copyright © 2016 Elsevier B.V. All rights reserved.

Transfer of chirality from light to a Disperse Red 1 molecular glass surface.

PubMed

Mazaheri, Leila; Lebel, Olivier; Nunzi, Jean-Michel

2017-12-01

Chiral structures and materials interact with light in well-documented ways, but light can also interact with achiral materials to generate chirality by inscribing its asymmetric configuration on photoresponsive materials, such as azobenzene derivatives. While it is thus possible to generate both two-dimensional (2D) and three-dimensional (3D) chirality, 2D chirality is especially attractive because of its non-reciprocity. Herein, 2D chirality is induced on the surface of a glass-forming Disperse Red 1 derivative by irradiation with a single laser beam, yielding crossed spontaneous surface relief gratings with different pitches. Azimuth rotations up to 10° have been observed, and the absence of 3D chirality has been confirmed. This method thus allows generating non-reciprocal planar chiral objects by a simple, single irradiation process on a thin film of a material that can easily be processed over large areas or onto small objects.

Inversion of Supramolecular Chirality by Sonication-Induced Organogelation

PubMed Central

Maity, Sibaprasad; Das, Priyadip; Reches, Meital

2015-01-01

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

Chirality Differentiation by Diffusion in Chiral Nematic Liquid Crystals

NASA Astrophysics Data System (ADS)

Jiang, Jinghua; Yang, Deng-Ke

2017-01-01

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

Chiral signs of TPPS co-assemblies with chiral gelators: role of molecular and supramolecular chirality.

PubMed

Wang, Qiuling; Zhang, Li; Yang, Dong; Li, Tiesheng; Liu, Minghua

2016-10-13

A dianionic tetrakis(4-sulfonatophenyl)porphyrin (TPPS) self-assembled into J-aggregates when it co-assembled with a chiral cationic amphiphile via supramolecular gelation. The chiral signs of TPPS J aggregates followed the supramolecular chirality of amphiphilic assemblies rather than the molecular chirality of the amphiphile.

Chiral fiber sensors

NASA Astrophysics Data System (ADS)

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

2010-04-01

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

Zwitterionic chiral stationary phases based on cinchona and chiral sulfonic acids for the direct stereoselective separation of amino acids and other amphoteric compounds.

PubMed

Zhang, Tong; Holder, Emilie; Franco, Pilar; Lindner, Wolfgang

2014-06-01

An extensive series of free amino acids and analogs were directly resolved into enantiomers (and stereoisomers where appropriate) by HPLC on zwitterionic chiral stationary phases (Chiralpak ZWIX(+) and Chiralpak ZWIX(-)). The interaction and chiral recognition mechanisms were based on the synergistic double ion-paring process between the analyte and the chiral selectors. The chiral separation and elution order were found to be predictable for primary α-amino acids with apolar aliphatic side chains. A systematic investigation was undertaken to gain an insight into the influence of the structural features on the enantiorecognition. The presence of polar and/or aromatic groups in the analyte structure is believed to tune the double ion-paring equilibrium by the involvement of the secondary interaction forces such as hydrogen bonding, Van der Waals forces and π-π stacking in concert with steric parameters. The ZWIX chiral columns were able to separate enantiomers and stereoisomers of various amphoteric compounds with no need for precolumn derivatization. Column switching between ZWIX(+) and ZWIX(-) is believed to be an instrumental tool to reverse or control the enantiomers elution order, due to the complementarity of the applied chiral selectors. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Ξ* and Ωη Interaction Within a Chiral Unitary Approach

NASA Astrophysics Data System (ADS)

Xu, Si-Qi; Xie, Ju-Jun; Chen, Xu-Rong; Jia, Duo-Jie

2016-01-01

In this work we study the interaction of the coupled channels Ωη and {\\Xi}\\ast\\bar{K} within the chiral unitary approach. The systems under consideration have total isospins 0, strangeness S = -3, and spin 3/2. We study the s wave interaction which implies that the possible resonances generated in the system can have spin-parity JP = 3/2-. The unitary amplitudes in coupled channels develop poles that can be associated with some known baryonic resonances. We find there is a dynamically generated 3/2- Ω state with mass around 1800 MeV, which is in agreement with the predictions of the five-quark model. Supported by the National Basic Research Program (973 Program Grant No. 2014CB845406), and the National Natural Science Foundation of China under Grant Nos. 11475227, 11265014, and the Open Project Program of State Key Laboratory of Theoretical Physics, Institute of Theoretical Physics, Chinese Academy of Sciences, China No. Y5KF151CJ1

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

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. © 2015 Wiley Periodicals, Inc.

Nucleon form factors in dispersively improved chiral effective field theory. II. Electromagnetic form factors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alarcon, J. M.; Weiss, C.

We study the nucleon electromagnetic form factors (EM FFs) using a recently developed method combining Chiral Effective Field Theory (more » $$\\chi$$EFT) and dispersion analysis. The spectral functions on the two-pion cut at $$t > 4 M_\\pi^2$$ are constructed using the elastic unitarity relation and an $N/D$ representation. $$\\chi$$EFT is used to calculate the real unctions $$J_\\pm^1 (t) = f_\\pm^1(t)/F_\\pi(t)$$ (ratios of the complex $$\\pi\\pi \\rightarrow N \\bar N$$ partial-wave amplitudes and the timelike pion FF), which are free of $$\\pi\\pi$$ rescattering. Rescattering effects are included through the empirical timelike pion FF $$|F_\\pi(t)|^2$$. The method allows us to compute the isovector EM spectral functions up to $$t \\sim 1$$ GeV$^2$ with controlled accuracy (LO, NLO, and partial N2LO). With the spectral functions we calculate the isovector nucleon EM FFs and their derivatives at $t = 0$ (EM radii, moments) using subtracted dispersion relations. We predict the values of higher FF derivatives with minimal uncertainties and explain their collective behavior. Finally, we estimate the individual proton and neutron FFs by adding an empirical parametrization of the isoscalar sector. Excellent agreement with the present low-$Q^2$ FF data is achieved up to $$\\sim$$0.5 GeV$^2$ for $$G_E$$, and up to $$\\sim$$0.2 GeV$^2$ for $$G_M$$. Our results can be used to guide the analysis of low-$Q^2$ elastic scattering data and the extraction of the proton charge radius.« less

Nucleon form factors in dispersively improved chiral effective field theory. II. Electromagnetic form factors

DOE PAGES

Alarcon, J. M.; Weiss, C.

2018-05-08

We study the nucleon electromagnetic form factors (EM FFs) using a recently developed method combining Chiral Effective Field Theory (more » $$\\chi$$EFT) and dispersion analysis. The spectral functions on the two-pion cut at $$t > 4 M_\\pi^2$$ are constructed using the elastic unitarity relation and an $N/D$ representation. $$\\chi$$EFT is used to calculate the real unctions $$J_\\pm^1 (t) = f_\\pm^1(t)/F_\\pi(t)$$ (ratios of the complex $$\\pi\\pi \\rightarrow N \\bar N$$ partial-wave amplitudes and the timelike pion FF), which are free of $$\\pi\\pi$$ rescattering. Rescattering effects are included through the empirical timelike pion FF $$|F_\\pi(t)|^2$$. The method allows us to compute the isovector EM spectral functions up to $$t \\sim 1$$ GeV$^2$ with controlled accuracy (LO, NLO, and partial N2LO). With the spectral functions we calculate the isovector nucleon EM FFs and their derivatives at $t = 0$ (EM radii, moments) using subtracted dispersion relations. We predict the values of higher FF derivatives with minimal uncertainties and explain their collective behavior. Finally, we estimate the individual proton and neutron FFs by adding an empirical parametrization of the isoscalar sector. Excellent agreement with the present low-$Q^2$ FF data is achieved up to $$\\sim$$0.5 GeV$^2$ for $$G_E$$, and up to $$\\sim$$0.2 GeV$^2$ for $$G_M$$. Our results can be used to guide the analysis of low-$Q^2$ elastic scattering data and the extraction of the proton charge radius.« less

Realization of highly efficient polymer solar cell based on PBDTTT-EFT and [71]PCBM

NASA Astrophysics Data System (ADS)

Bharti, Vishal; Chand, Suresh; Dutta, Viresh

2018-04-01

In this work, we have fabricated highly efficient polymer solar cells based on the blend of PBDTTT-EFT:PC71BM in the inverted device configuration. By using low temperature processed zinc oxide (ZnO) nanoparticles as an electron-transport layer (ETL) and 1,8-diiodooctane (DIO) as additive in chlorobenzene (CB) solvent we have achieved PCE of 9.43% with an excellent short-circuit current density (Jsc) of 17.6 mAcm-2, open circuit voltage (Voc) of 0.80 V and fill factor (FF) of 0.67. These results reveals that addition of 3% DIO additive in CB solvent improve the morphology (lower charge carrier recombination and better metal/organic semiconductor interface) and provide uniform interpenetrating networks in PBDTTT-EFT:PC71BM blend active layer.

Universal dissymmetry and the origin of biomolecular chirality.

PubMed

Mason, S F

1987-01-01

Handed systems are distributed over four general domains. These span the fundamental particles, the molecular enantiomers, the crystal enantiomorphs, and the spiral galaxies. The characterisation of the molecular enantiomers followed from the identification of the crystal enantiomorphs and revealed a chiral homogeneity in the biomolecules of the organic world. The origin of the homogeneity has been variously ascribed to a universal dissymmetric force, from Pasteur, or to a chance choice of the initial enantiomer perpetuated by the stereoselection of diastereomer production with recycling, from Fischer's "key and lock" hypothesis. The classical chiral fields identified by Curie require a particular time or location on the Earth's surface for a determinate molecular enantioselection, as do the weak charged current agencies of the non-classical weak interaction. The weak neutral current of the electroweak interaction provides a constant and uniform chiral agency which favours both the L-series of amino acids and polypeptides and the parent aldotriose of the D-series of sugars. The enantiomeric bias of the electroweak interaction is small at the molecular level: it may become significant either as a trigger-perturbation guiding the transition from a metastable autocatalytic racemic process to one of the two constituent enantiomeric reaction channels, or by cumulative amplification in a large chirally-homogeneous aggregate of enantiomer units.

Supernovae, neutrinos and the chirality of amino acids.

PubMed

Boyd, Richard N; Kajino, Toshitaka; Onaka, Takashi

2011-01-01

A mechanism for creating an enantioenrichment in the amino acids, the building blocks of the proteins, that involves global selection of one handedness by interactions between the amino acids and neutrinos from core-collapse supernovae is defined. The chiral selection involves the dependence of the interaction cross sections on the orientations of the spins of the neutrinos and the (14)N nuclei in the amino acids, or in precursor molecules, which in turn couple to the molecular chirality. It also requires an asymmetric distribution of neutrinos emitted from the supernova. The subsequent chemical evolution and galactic mixing would ultimately populate the Galaxy with the selected species. The resulting amino acids could either be the source thereof on Earth, or could have triggered the chirality that was ultimately achieved for Earth's proteinaceous amino acids.

Orion EFT-1 Catalytic Tile Experiment Overview and Flight Measurements

NASA Technical Reports Server (NTRS)

Salazar, Giovanni; Amar, Adam; Hyatt, Andrew; Rezin, Marc D.

2016-01-01

This paper describes the design and results of a surface catalysis flight experiment flown on the Orion Multipurpose Crew Vehicle during Exploration Flight Test 1 (EFT1). Similar to previous Space Shuttle catalytic tile experiments, the present test consisted of a highly catalytic coating applied to an instrumented TPS tile. However, the present catalytic tile experiment contained significantly more instrumentation in order to better resolve the heating overshoot caused by the change in surface catalytic efficiency at the interface between two distinct materials. In addition to collecting data with unprecedented spatial resolution of the "overshoot" phenomenon, the experiment was also designed to prove if such a catalytic overshoot would be seen in turbulent flow in high enthalpy regimes. A detailed discussion of the results obtained during EFT1 is presented, as well as the challenges associated with data interpretation of this experiment. Results of material testing carried out in support of this flight experiment are also shown. Finally, an inverse heat conduction technique is employed to reconstruct the flight environments at locations upstream and along the catalytic coating. The data and analysis presented in this work will greatly contribute to our understanding of the catalytic "overshoot" phenomenon, and have a significant impact on the design of future spacecraft.

Chiral magnetism of magnetic adatoms generated by Rashba electrons

NASA Astrophysics Data System (ADS)

Bouaziz, Juba; dos Santos Dias, Manuel; Ziane, Abdelhamid; Benakki, Mouloud; Blügel, Stefan; Lounis, Samir

2017-02-01

We investigate long-range chiral magnetic interactions among adatoms mediated by surface states spin-splitted by spin-orbit coupling. Using the Rashba model, the tensor of exchange interactions is extracted wherein a thepseudo-dipolar interaction is found, in addition to the usual isotropic exchange interaction and the Dzyaloshinskii-Moriya interaction. We find that, despite the latter interaction, collinear magnetic states can still be stabilized by the pseudo-dipolar interaction. The interadatom distance controls the strength of these terms, which we exploit to design chiral magnetism in Fe nanostructures deposited on a Au(111) surface. We demonstrate that these magnetic interactions are related to superpositions of the out-of-plane and in-plane components of the skyrmionic magnetic waves induced by the adatoms in the surrounding electron gas. We show that, even if the interatomic distance is large, the size and shape of the nanostructures dramatically impacts on the strength of the magnetic interactions, thereby affecting the magnetic ground state. We also derive an appealing connection between the isotropic exchange interaction and the Dzyaloshinskii-Moriya interaction, which relates the latter to the first-order change of the former with respect to spin-orbit coupling. This implies that the chirality defined by the direction of the Dzyaloshinskii-Moriya vector is driven by the variation of the isotropic exchange interaction due to the spin-orbit interaction.

77 FR 71035 - Financial Management Service; Proposed Collection of Information: Electronic Funds Transfer (EFT...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-11-28

... DEPARTMENT OF THE TREASURY Fiscal Service Financial Management Service; Proposed Collection of Information: Electronic Funds Transfer (EFT) Market Research Study AGENCY: Financial Management Service, Fiscal Service, Treasury. ACTION: Notice and Request for comments. SUMMARY: The Financial Management...

Chiral superconductors.

PubMed

Kallin, Catherine; Berlinsky, John

2016-05-01

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

Enantiospecific Detection of Chiral Nanosamples Using Photoinduced Force

NASA Astrophysics Data System (ADS)

Kamandi, Mohammad; Albooyeh, Mohammad; Guclu, Caner; Veysi, Mehdi; Zeng, Jinwei; Wickramasinghe, Kumar; Capolino, Filippo

2017-12-01

We propose a high-resolution microscopy technique for enantiospecific detection of chiral samples down to sub-100-nm size based on force measurement. We delve into the differential photoinduced optical force Δ F exerted on an achiral probe in the vicinity of a chiral sample when left and right circularly polarized beams separately excite the sample-probe interactive system. We analytically prove that Δ F is entangled with the enantiomer type of the sample enabling enantiospecific detection of chiral inclusions. Moreover, we demonstrate that Δ F is linearly dependent on both the chiral response of the sample and the electric response of the tip and is inversely related to the quartic power of probe-sample distance. We provide physical insight into the transfer of optical activity from the chiral sample to the achiral tip based on a rigorous analytical approach. We support our theoretical achievements by several numerical examples highlighting the potential application of the derived analytic properties. Lastly, we demonstrate the sensitivity of our method to enantiospecify nanoscale chiral samples with chirality parameter on the order of 0.01 and discuss how the sensitivity of our proposed technique can be further improved.

Stardust, Supernovae and the Chirality of the Amino Acids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boyd, R N; Kajino, T; Onaka, T

A mechanism for creating enantiomerism in the amino acids, the building blocks of the proteins, that involves global selection of one chirality by interactions between the amino acids and neutrinos from core-collapse supernovae is described. The selection involves the dependence of the interaction cross sections on the orientations of the spins of the neutrinos and the 14N nuclei in the amino acids, or in precursor molecules, which in turn couple to the molecular chirality. The subsequent chemical evolution and galactic mixing would ultimately populate the Galaxy with the selected species. The resulting amino acids could either be the source thereofmore » on Earth, or could have triggered the chirality that was ultimately achieved for Earth's amino acids.« less

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

PubMed

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

2018-05-16

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

Chiral magnetic effect without chirality source in asymmetric Weyl semimetals

NASA Astrophysics Data System (ADS)

Kharzeev, Dmitri E.; Kikuchi, Yuta; Meyer, René

2018-05-01

We describe a new type of the chiral magnetic effect (CME) that should occur in Weyl semimetals (WSMs) with an asymmetry in the dispersion relations of the left- and right-handed (LH and RH) chiral Weyl fermions. In such materials, time-dependent pumping of electrons from a non-chiral external source can generate a non-vanishing chiral chemical potential. This is due to the different capacities of the LH and RH chiral Weyl cones arising from the difference in the density of states in the LH and RH cones. The chiral chemical potential then generates, via the chiral anomaly, a current along the direction of an applied magnetic field even in the absence of an external electric field. The source of chirality imbalance in this new setup is thus due to the band structure of the system and the presence of (non-chiral) electron source, and not due to the parallel electric and magnetic fields. We illustrate the effect by an argument based on the effective field theory, and by the chiral kinetic theory calculation for a rotationally invariant WSM with different Fermi velocities in the left and right chiral Weyl cones; we also consider the case of a WSM with Weyl nodes at different energies. We argue that this effect is generically present in WSMs with different dispersion relations for LH and RH chiral Weyl cones, such as SrSi2 recently predicted as a WSM with broken inversion and mirror symmetries, as long as the chiral relaxation time is much longer than the transport scattering time.

Supernovae, Neutrinos and the Chirality of Amino Acids

PubMed Central

Boyd, Richard N.; Kajino, Toshitaka; Onaka, Takashi

2011-01-01

A mechanism for creating an enantioenrichment in the amino acids, the building blocks of the proteins, that involves global selection of one handedness by interactions between the amino acids and neutrinos from core-collapse supernovae is defined. The chiral selection involves the dependence of the interaction cross sections on the orientations of the spins of the neutrinos and the 14N nuclei in the amino acids, or in precursor molecules, which in turn couple to the molecular chirality. It also requires an asymmetric distribution of neutrinos emitted from the supernova. The subsequent chemical evolution and galactic mixing would ultimately populate the Galaxy with the selected species. The resulting amino acids could either be the source thereof on Earth, or could have triggered the chirality that was ultimately achieved for Earth’s proteinaceous amino acids. PMID:21747686

Application of classical models of chirality to optical rectification

NASA Astrophysics Data System (ADS)

Wang, Xiao-Ou; Gong, Li-Jing; Li, Chun-Fei

2008-08-01

Classical models of chirality are used to investigate the optical rectification effect in chiral molecular media. Calculation of the zero frequency first hyperpolarizabilities of chiral molecules with different structures is performed and applied to the derivation of a dc electric-dipole polarization. The expression of second-order nonlinear static-electric-dipole susceptibilities is obtained by theoretical derivation in the isotropic chiral thin films. The microscopic mechanism producing optical rectification is analyzed in view of this calculation. We find that optical rectification is derived from interaction between the electric field gradient (spatial dispersion) and chiral molecules in optically active liquids and solution by our calculation, which is consistent with the result given by Woźniak and Wagnière [Opt. Commun. 114, 131 (1995)]: The optical rectification depends on the fourth-order electric-dipole susceptibilities.

Electric-field–induced assembly and propulsion of chiral colloidal clusters

PubMed Central

Ma, Fuduo; Wang, Sijia; Wu, David T.; Wu, Ning

2015-01-01

Chiral molecules with opposite handedness exhibit distinct physical, chemical, or biological properties. They pose challenges as well as opportunities in understanding the phase behavior of soft matter, designing enantioselective catalysts, and manufacturing single-handed pharmaceuticals. Microscopic particles, arranged in a chiral configuration, could also exhibit unusual optical, electric, or magnetic responses. Here we report a simple method to assemble achiral building blocks, i.e., the asymmetric colloidal dimers, into a family of chiral clusters. Under alternating current electric fields, two to four lying dimers associate closely with a central standing dimer and form both right- and left-handed clusters on a conducting substrate. The cluster configuration is primarily determined by the induced dipolar interactions between constituent dimers. Our theoretical model reveals that in-plane dipolar repulsion between petals in the cluster favors the achiral configuration, whereas out-of-plane attraction between the central dimer and surrounding petals favors a chiral arrangement. It is the competition between these two interactions that dictates the final configuration. The theoretical chirality phase diagram is found to be in excellent agreement with experimental observations. We further demonstrate that the broken symmetry in chiral clusters induces an unbalanced electrohydrodynamic flow surrounding them. As a result, they rotate in opposite directions according to their handedness. Both the assembly and propulsion mechanisms revealed here can be potentially applied to other types of asymmetric particles. Such kinds of chiral colloids will be useful for fabricating metamaterials, making model systems for both chiral molecules and active matter, or building propellers for microscale transport. PMID:25941383

Emergent chirality in the electric polarization texture of titanate superlattices.

PubMed

Shafer, Padraic; García-Fernández, Pablo; Aguado-Puente, Pablo; Damodaran, Anoop R; Yadav, Ajay K; Nelson, Christopher T; Hsu, Shang-Lin; Wojdeł, Jacek C; Íñiguez, Jorge; Martin, Lane W; Arenholz, Elke; Junquera, Javier; Ramesh, Ramamoorthy

2018-01-30

Chirality is a geometrical property by which an object is not superimposable onto its mirror image, thereby imparting a handedness. Chirality determines many important properties in nature-from the strength of the weak interactions according to the electroweak theory in particle physics to the binding of enzymes with naturally occurring amino acids or sugars, reactions that are fundamental for life. In condensed matter physics, the prediction of topologically protected magnetic skyrmions and related spin textures in chiral magnets has stimulated significant research. If the magnetic dipoles were replaced by their electrical counterparts, then electrically controllable chiral devices could be designed. Complex oxide BaTiO 3 /SrTiO 3 nanocomposites and PbTiO 3 /SrTiO 3 superlattices are perfect candidates, since "polar vortices," in which a continuous rotation of ferroelectric polarization spontaneously forms, have been recently discovered. Using resonant soft X-ray diffraction, we report the observation of a strong circular dichroism from the interaction between circularly polarized light and the chiral electric polarization texture that emerges in PbTiO 3 /SrTiO 3 superlattices. This hallmark of chirality is explained by a helical rotation of electric polarization that second-principles simulations predict to reside within complex 3D polarization textures comprising ordered topological line defects. The handedness of the texture can be topologically characterized by the sign of the helicity number of the chiral line defects. This coupling between the optical and novel polar properties could be exploited to encode chiral signatures into photon or electron beams for information processing.

Electric-field-induced assembly and propulsion of chiral colloidal clusters.

PubMed

Ma, Fuduo; Wang, Sijia; Wu, David T; Wu, Ning

2015-05-19

Chiral molecules with opposite handedness exhibit distinct physical, chemical, or biological properties. They pose challenges as well as opportunities in understanding the phase behavior of soft matter, designing enantioselective catalysts, and manufacturing single-handed pharmaceuticals. Microscopic particles, arranged in a chiral configuration, could also exhibit unusual optical, electric, or magnetic responses. Here we report a simple method to assemble achiral building blocks, i.e., the asymmetric colloidal dimers, into a family of chiral clusters. Under alternating current electric fields, two to four lying dimers associate closely with a central standing dimer and form both right- and left-handed clusters on a conducting substrate. The cluster configuration is primarily determined by the induced dipolar interactions between constituent dimers. Our theoretical model reveals that in-plane dipolar repulsion between petals in the cluster favors the achiral configuration, whereas out-of-plane attraction between the central dimer and surrounding petals favors a chiral arrangement. It is the competition between these two interactions that dictates the final configuration. The theoretical chirality phase diagram is found to be in excellent agreement with experimental observations. We further demonstrate that the broken symmetry in chiral clusters induces an unbalanced electrohydrodynamic flow surrounding them. As a result, they rotate in opposite directions according to their handedness. Both the assembly and propulsion mechanisms revealed here can be potentially applied to other types of asymmetric particles. Such kinds of chiral colloids will be useful for fabricating metamaterials, making model systems for both chiral molecules and active matter, or building propellers for microscale transport.

Enantioselective Biotransformation of Chiral Persistent Organic Pollutants.

PubMed

Zhang, Ying; Ye, Jing; Liu, Min

2017-01-01

Enantiomers of chiral compounds commonly undergo enantioselective transformation in most biologically mediated processes. As chiral persistent organic pollutants (POPs) are extensively distributed in the environment, differences between enantiomers in biotransformation should be carefully considered to obtain exact enrichment and specific health risks. This review provides an overview of in vivo biotransformation of chiral POPs currently indicated in the Stockholm Convention and their chiral metabolites. Peer-reviewed journal articles focused on the research question were thoroughly searched. A set of inclusion and exclusion criteria were developed to identify relevant studies. We mainly compared the results from different animal models under controlled laboratory conditions to show the difference between enantiomers in terms of distinct transformation potential. Interactions with enzymes involved in enantioselective biotransformation, especially cytochrome P450 (CYP), were discussed. Further research areas regarding this issue were proposed. Limited evidence for a few POPs has been found in 30 studies. Enantioselective biotransformation of α-hexachlorocyclohexane (α-HCH), chlordane, dichlorodiphenyltrichloroethane (DDT), heptachlor, hexabromocyclododecane (HBCD), polychlorinated biphenyls (PCBs), and toxaphene, has been investigated using laboratory mammal, fish, bird, and worm models. Tissue and excreta distributions, as well as bioaccumulation and elimination kinetics after administration of racemate and pure enantiomers, have been analyzed in these studies. Changes in enantiomeric fractions have been considered as an indicator of enantioselective biotransformation of chiral POPs in most studies. Results of different laboratory animal models revealed that chiral POP biotransformation is seriously affected by chirality. Pronounced results of species-, tissue-, gender-, and individual-dependent differences are observed in in vivo biotransformation of chiral POPs

Single-particle potential of the Λ hyperon in nuclear matter with chiral effective field theory NLO interactions including effects of Y N N three-baryon interactions

NASA Astrophysics Data System (ADS)

Kohno, M.

2018-03-01

Adopting hyperon-nucleon and hyperon-nucleon-nucleon interactions parametrized in chiral effective field theory, single-particle potentials of the Λ and Σ hyperons are evaluated in symmetric nuclear matter and in pure neutron matter within the framework of lowest-order Bruckner theory. The chiral NLO interaction bears strong Λ N -Σ N coupling. Although the Λ potential is repulsive if the coupling is switched off, the Λ N -Σ N correlation brings about the attraction consistent with empirical data. The Σ potential is repulsive, which is also consistent with empirical information. The interesting result is that the Λ potential becomes shallower beyond normal density. This provides the possibility of solving the hyperon puzzle without introducing ad hoc assumptions. The effects of the Λ N N -Λ N N and Λ N N -Σ N N three-baryon forces are considered. These three-baryon forces are first reduced to normal-ordered effective two-baryon interactions in nuclear matter and then incorporated in the G -matrix equation. The repulsion from the Λ N N -Λ N N interaction is of the order of 5 MeV at normal density and becomes larger with increasing density. The effects of the Λ N N -Σ N N coupling compensate the repulsion at normal density. The net effect of the three-baryon interactions on the Λ single-particle potential is repulsive at higher densities.

Neuronal growth on L- and D-cysteine self-assembled monolayers reveals neuronal chiral sensitivity.

PubMed

Baranes, Koby; Moshe, Hagay; Alon, Noa; Schwartz, Shmulik; Shefi, Orit

2014-05-21

Studying the interaction between neuronal cells and chiral molecules is fundamental for the design of novel biomaterials and drugs. Chirality influences all biological processes that involve intermolecular interaction. One common method used to study cellular interactions with different enantiomeric targets is the use of chiral surfaces. Based on previous studies that demonstrated the importance of cysteine in the nervous system, we studied the effect of L- and D-cysteine on single neuronal growth. L-Cysteine, which normally functions as a neuromodulator or a neuroprotective antioxidant, causes damage at elevated levels, which may occur post trauma. In this study, we grew adult neurons in culture enriched with L- and D-cysteine as free compounds or as self-assembled monolayers of chiral surfaces and examined the effect on the neuronal morphology and adhesion. Notably, we have found that exposure to the L-cysteine enantiomer inhibited, and even prevented, neuronal attachment more severely than exposure to the D-cysteine enantiomer. Atop the L-cysteine surfaces, neuronal growth was reduced and degenerated. Since the cysteine molecules were attached to the surface via the thiol groups, the neuronal membrane was exposed to the molecular chiral site. Thus, our results have demonstrated high neuronal chiral sensitivity, revealing chiral surfaces as indirect regulators of neuronal cells and providing a reference for studying chiral drugs.

Delta Mariner arrival with EFT-1 Booster

NASA Image and Video Library

2014-03-03

CAPE CANAVERAL, Fla. – The United Launch Alliance barge Delta Mariner enters Port Canaveral in Florida. The barge is carrying two of the booster stages for the Delta IV Heavy rocket slated for Orion's Exploration Flight Test-1, or EFT-1. Orion is the exploration spacecraft designed to carry astronauts to destinations not yet explored by humans. It will have emergency abort capability, sustain the crew during space travel and provide safe re-entry from deep-space return velocities. The first unpiloted test flight of Orion is scheduled to launch in September 2014 atop a Delta IV Heavy rocket and in 2017 on NASA’s Space Launch System rocket. For more information, visit www.nasa.gov/orion. Photo credit: NASA/Frankie Martin

Delta Mariner arrival with EFT-1 Booster

NASA Image and Video Library

2014-03-03

CAPE CANAVERAL, Fla. – The United Launch Alliance barge Delta Mariner is secured to the dock in Port Canaveral in Florida. The barge is carrying two of the booster stages for the Delta IV Heavy rocket slated for Orion's Exploration Flight Test-1, or EFT-1. Orion is the exploration spacecraft designed to carry astronauts to destinations not yet explored by humans. It will have emergency abort capability, sustain the crew during space travel and provide safe re-entry from deep-space return velocities. The first unpiloted test flight of Orion is scheduled to launch in September 2014 atop a Delta IV Heavy rocket and in 2017 on NASA’s Space Launch System rocket. For more information, visit www.nasa.gov/orion. Photo credit: NASA/Frankie Martin

Delta Mariner arrival with EFT-1 Booster

NASA Image and Video Library

2014-03-03

CAPE CANAVERAL, Fla. – The United Launch Alliance barge Delta Mariner prepares to dock in Port Canaveral in Florida. The barge is carrying two of the booster stages for the Delta IV Heavy rocket slated for Orion's Exploration Flight Test-1, or EFT-1. Orion is the exploration spacecraft designed to carry astronauts to destinations not yet explored by humans. It will have emergency abort capability, sustain the crew during space travel and provide safe re-entry from deep-space return velocities. The first unpiloted test flight of Orion is scheduled to launch in September 2014 atop a Delta IV Heavy rocket and in 2017 on NASA’s Space Launch System rocket. For more information, visit www.nasa.gov/orion. Photo credit: NASA/Frankie Martin

Delta Mariner arrival with EFT-1 Booster

NASA Image and Video Library

2014-03-03

CAPE CANAVERAL, Fla. – The United Launch Alliance barge Delta Mariner approaches the mouth of Port Canaveral in Florida. The barge is carrying two of the booster stages for the Delta IV Heavy rocket slated for Orion's Exploration Flight Test-1, or EFT-1. Orion is the exploration spacecraft designed to carry astronauts to destinations not yet explored by humans. It will have emergency abort capability, sustain the crew during space travel and provide safe re-entry from deep-space return velocities. The first unpiloted test flight of Orion is scheduled to launch in September 2014 atop a Delta IV Heavy rocket and in 2017 on NASA’s Space Launch System rocket. For more information, visit www.nasa.gov/orion. Photo credit: NASA/Frankie Martin

Delta Mariner arrival with EFT-1 Booster

NASA Image and Video Library

2014-03-03

CAPE CANAVERAL, Fla. – The United Launch Alliance barge Delta Mariner nears the dock in Port Canaveral in Florida. The barge is carrying two of the booster stages for the Delta IV Heavy rocket slated for Orion's Exploration Flight Test-1, or EFT-1. Orion is the exploration spacecraft designed to carry astronauts to destinations not yet explored by humans. It will have emergency abort capability, sustain the crew during space travel and provide safe re-entry from deep-space return velocities. The first unpiloted test flight of Orion is scheduled to launch in September 2014 atop a Delta IV Heavy rocket and in 2017 on NASA’s Space Launch System rocket. For more information, visit www.nasa.gov/orion. Photo credit: NASA/Frankie Martin

Delta Mariner arrival with EFT-1 Booster

NASA Image and Video Library

2014-03-03

CAPE CANAVERAL, Fla. – The United Launch Alliance barge Delta Mariner travels through Port Canaveral in Florida. The barge is carrying two of the booster stages for the Delta IV Heavy rocket slated for Orion's Exploration Flight Test-1, or EFT-1. Orion is the exploration spacecraft designed to carry astronauts to destinations not yet explored by humans. It will have emergency abort capability, sustain the crew during space travel and provide safe re-entry from deep-space return velocities. The first unpiloted test flight of Orion is scheduled to launch in September 2014 atop a Delta IV Heavy rocket and in 2017 on NASA’s Space Launch System rocket. For more information, visit www.nasa.gov/orion. Photo credit: NASA/Frankie Martin

Delta Mariner arrival with EFT-1 Booster

NASA Image and Video Library

2014-03-03

CAPE CANAVERAL, Fla. – The United Launch Alliance barge Delta Mariner docks in Port Canaveral in Florida. The barge is carrying two of the booster stages for the Delta IV Heavy rocket slated for Orion's Exploration Flight Test-1, or EFT-1. Orion is the exploration spacecraft designed to carry astronauts to destinations not yet explored by humans. It will have emergency abort capability, sustain the crew during space travel and provide safe re-entry from deep-space return velocities. The first unpiloted test flight of Orion is scheduled to launch in September 2014 atop a Delta IV Heavy rocket and in 2017 on NASA’s Space Launch System rocket. For more information, visit www.nasa.gov/orion. Photo credit: NASA/Frankie Martin

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.

Mitochondrial EFTs defects in juvenile-onset Leigh disease, ataxia, neuropathy, and optic atrophy

PubMed Central

Ahola, Sofia; Isohanni, Pirjo; Euro, Liliya; Brilhante, Virginia; Palotie, Aarno; Pihko, Helena; Lönnqvist, Tuula; Lehtonen, Tanita; Laine, Jukka; Tyynismaa, Henna

2014-01-01

Objective: We report novel defects of mitochondrial translation elongation factor Ts (EFTs), with high carrier frequency in Finland and expand the manifestations of this disease group from infantile cardiomyopathy to juvenile neuropathy/encephalopathy disorders. Methods: DNA analysis, whole-exome analysis, protein biochemistry, and protein modeling. Results: We used whole-exome sequencing to find the genetic cause of infantile-onset mitochondrial cardiomyopathy, progressing to juvenile-onset Leigh syndrome, neuropathy, and optic atrophy in 2 siblings. We found novel compound heterozygous mutations, c.944G>A [p.C315Y] and c.856C>T [p.Q286X], in the TSFM gene encoding mitochondrial EFTs. The same p.Q286X variant was found as compound heterozygous with a splice site change in a patient from a second family, with juvenile-onset optic atrophy, peripheral neuropathy, and ataxia. Our molecular modeling predicted the coding-region mutations to cause protein instability, which was experimentally confirmed in cultured patient cells, with mitochondrial translation defect and lacking EFTs. Only a single TSFM mutation has been previously described in different populations, leading to an infantile fatal multisystem disorder with cardiomyopathy. Sequence data from 35,000 Finnish population controls indicated that the heterozygous carrier frequency of p.Q286X change was exceptionally high in Finland, 1:80, but no homozygotes were found in the population, in our mitochondrial disease patient collection, or in an intrauterine fetal death material, suggesting early developmental lethality of the homozygotes. Conclusions: We show that in addition to early-onset cardiomyopathy, TSFM mutations should be considered in childhood and juvenile encephalopathies with optic and/or peripheral neuropathy, ataxia, or Leigh disease. PMID:25037205

Mitochondrial EFTs defects in juvenile-onset Leigh disease, ataxia, neuropathy, and optic atrophy.

PubMed

Ahola, Sofia; Isohanni, Pirjo; Euro, Liliya; Brilhante, Virginia; Palotie, Aarno; Pihko, Helena; Lönnqvist, Tuula; Lehtonen, Tanita; Laine, Jukka; Tyynismaa, Henna; Suomalainen, Anu

2014-08-19

We report novel defects of mitochondrial translation elongation factor Ts (EFTs), with high carrier frequency in Finland and expand the manifestations of this disease group from infantile cardiomyopathy to juvenile neuropathy/encephalopathy disorders. DNA analysis, whole-exome analysis, protein biochemistry, and protein modeling. We used whole-exome sequencing to find the genetic cause of infantile-onset mitochondrial cardiomyopathy, progressing to juvenile-onset Leigh syndrome, neuropathy, and optic atrophy in 2 siblings. We found novel compound heterozygous mutations, c.944G>A [p.C315Y] and c.856C>T [p.Q286X], in the TSFM gene encoding mitochondrial EFTs. The same p.Q286X variant was found as compound heterozygous with a splice site change in a patient from a second family, with juvenile-onset optic atrophy, peripheral neuropathy, and ataxia. Our molecular modeling predicted the coding-region mutations to cause protein instability, which was experimentally confirmed in cultured patient cells, with mitochondrial translation defect and lacking EFTs. Only a single TSFM mutation has been previously described in different populations, leading to an infantile fatal multisystem disorder with cardiomyopathy. Sequence data from 35,000 Finnish population controls indicated that the heterozygous carrier frequency of p.Q286X change was exceptionally high in Finland, 1:80, but no homozygotes were found in the population, in our mitochondrial disease patient collection, or in an intrauterine fetal death material, suggesting early developmental lethality of the homozygotes. We show that in addition to early-onset cardiomyopathy, TSFM mutations should be considered in childhood and juvenile encephalopathies with optic and/or peripheral neuropathy, ataxia, or Leigh disease. © 2014 American Academy of Neurology.

Structural insights into two inorganic-organic hybrids based on chiral amino acids and polyoxomolybdates

NASA Astrophysics Data System (ADS)

Arefian, Mina; Mirzaei, Masoud; Eshtiagh-Hosseini, Hossein

2018-03-01

A new chiral inorganic-organic hybrid with the formula (L-His)2(H7CoMo6O24)·6H2O (1), based on natural amino acid and Anderson type polyoxomolybdate was synthesized through mild condition. The chiral L-histidine molecules induced chirality to the whole structure through various types of strong and unconventional hydrogen bond (HB) interactions (CH⋯O, NH⋯O and CH···π interactions), as well as bifurcated hydrogen bonds (BHBs) between L-histidine amino acid, hexamer water cluster molecules, and H7CoMo6O24·xH2O. Following, important non-covalent CH⋯O interactions is investigated in another chiral inorganic-organic hybrid structure, (L-Pro)3(PMo12O40).4.5H2O (2), in detail. The CH⋯O hydrogen bonds lead to a chiral network similar to the DNA strands affording a promising candidate to bio-inorganic studies.

In situ synthesis of di-n-butyl l-tartrate-boric acid complex chiral selector and its application in chiral microemulsion electrokinetic chromatography.

PubMed

Hu, Shaoqiang; Chen, Yonglei; Zhu, Huadong; Zhu, Jinhua; Yan, Na; Chen, Xingguo

2009-11-06

A novel procedure for in situ assembling a complex chiral selector, di-n-butyl l-tartrate-boric acid complex, by the reaction of di-n-butyl l-tartrate with boric acid in a running buffer was reported and its application in the enantioseparation of beta-blockers and structural related compounds by chiral microemulsion electrokinetic chromatography (MEEKC) has been demonstrated. In order to achieve a good enantioseparation, the effect of dibutyl l-tartrate and sodium tetraborate concentration, surfactant identity and concentration, cosurfactant, buffer pH and composition, organic modifiers, as well as applied voltage and capillary length were investigated. Ten pairs of enantiomers that could not be separated with only dibutyl l-tartrate, obtained good chiral separation using the complex chiral selector; among them, seven pairs could be baseline resolved under optimized experimental conditions. The fixation of chiral centers by the formation of five-membered rings, and being oppositely charged with basic analytes were thought to be the key factors giving the complex chiral selector a superior chiral recognition capability. The effect of the molecular structure of analytes on enantioseparation was discussed in terms of molecular interaction.

Chiral Spin Order in Kondo-Heisenberg Systems

NASA Astrophysics Data System (ADS)

Tsvelik, A. M.; Yevtushenko, O. M.

2017-12-01

We demonstrate that low dimensional Kondo-Heisenberg systems, consisting of itinerant electrons and localized magnetic moments (Kondo impurities), can be used as a principally new platform to realize scalar chiral spin order. The underlying physics is governed by a competition of the Ruderman-Kittel-Kosuya-Yosida (RKKY) indirect exchange interaction between the local moments with the direct Heisenberg one. When the direct exchange is weak and RKKY dominates, the isotropic system is in the disordered phase. A moderately large direct exchange leads to an Ising-type phase transition to the phase with chiral spin order. Our finding paves the way towards pioneering experimental realizations of the chiral spin liquid in systems with spontaneously broken time-reversal symmetry.

Membrane rafts stabilized by chiral liquid crystal correction to bare interfacial tension

NASA Astrophysics Data System (ADS)

Kang, Louis; Lubensky, T. C.

Lipid rafts are hypothesized to facilitate protein interaction, tension regulation, and trafficking in biological membranes, but the mechanisms responsible for their formation and maintenance are not clear. Recently, experiments showed that bidisperse mixtures of filamentous viruses can self-assemble into colloidal monolayers with thermodynamically stable rafts that exhibit chiral structure and repulsive interactions. We quantitatively explain these observations by modeling the membrane particles as chiral liquid crystals. Chiral twist promotes the formation of finite-sized rafts by decreasing the effective interfacial tension between rafts and background membrane. It also mediates a repulsion that distributes rafts evenly throughout the membrane. Although this system is composed of filamentous viruses whose aggregation is entropically driven by dextran depletants instead of phospholipids and cholesterol with prominent electrostatic interactions, colloidal and biological membranes share many of the same physical symmetries. Chiral twist can contribute to the behavior of both systems and may account for certain stereospecific effects observed in molecular membranes.

Optical Chirality in Nonlinear Optics: Application to High Harmonic Generation

NASA Astrophysics Data System (ADS)

Neufeld, Ofer; Cohen, Oren

2018-03-01

Optical chirality (OC)—one of the fundamental quantities of electromagnetic fields—corresponds to the instantaneous chirality of light. It has been utilized for exploring chiral light-matter interactions in linear optics, but has not yet been applied to nonlinear processes. Motivated to explore the role of OC in the generation of helically polarized high-order harmonics and attosecond pulses, we first separate the OC of transversal and paraxial beams to polarization and orbital terms. We find that the polarization-associated OC of attosecond pulses corresponds approximately to that of the pump in the quasimonochromatic case, but not in the multichromatic pump cases. We associate this discrepancy with the fact that the polarization OC of multichromatic pumps vary rapidly in time along the optical cycle. Thus, we propose new quantities, noninstantaneous polarization-associated OC, and time-scale-weighted polarization-associated OC, and show that these quantities link the chirality of multichromatic pumps and their generated attosecond pulses. The presented extension to OC theory should be useful for exploring various nonlinear chiral light-matter interactions. For example, it stimulates us to propose a tricircular pump for generation of highly elliptical attosecond pulses with a tunable ellipticity.

Optical Chirality in Nonlinear Optics: Application to High Harmonic Generation.

PubMed

Neufeld, Ofer; Cohen, Oren

2018-03-30

Optical chirality (OC)-one of the fundamental quantities of electromagnetic fields-corresponds to the instantaneous chirality of light. It has been utilized for exploring chiral light-matter interactions in linear optics, but has not yet been applied to nonlinear processes. Motivated to explore the role of OC in the generation of helically polarized high-order harmonics and attosecond pulses, we first separate the OC of transversal and paraxial beams to polarization and orbital terms. We find that the polarization-associated OC of attosecond pulses corresponds approximately to that of the pump in the quasimonochromatic case, but not in the multichromatic pump cases. We associate this discrepancy with the fact that the polarization OC of multichromatic pumps vary rapidly in time along the optical cycle. Thus, we propose new quantities, noninstantaneous polarization-associated OC, and time-scale-weighted polarization-associated OC, and show that these quantities link the chirality of multichromatic pumps and their generated attosecond pulses. The presented extension to OC theory should be useful for exploring various nonlinear chiral light-matter interactions. For example, it stimulates us to propose a tricircular pump for generation of highly elliptical attosecond pulses with a tunable ellipticity.

Chiral capillary electrophoresis and nuclear magnetic resonance investigation on the structure-enantioselectivity relationship in synthetic cyclopeptides as chiral selectors.

PubMed

De Lorenzi, E; Massolini, G; Molinari, P; Galbusera, C; Longhi, R; Marinzi, C; Consonni, R; Chiari, M

2001-04-01

In the present work, synthetic cyclohexa- and cycloheptapeptides previously singled out by a combinatorial chemistry approach have been evaluated as chiral selectors in capillary electrophoresis. By applying the countercurrent migration technique and employing a new adsorbed coating, a series of dinitrophenyl amino acids as well as some chiral compounds of pharmaceutical interest have been evaluated for enantiorecognition. The results thus obtained led to a deeper investigation of the chiral discrimination process, by carrying out nuclear magnetic resonance (NMR) studies on selected cyclopeptide-analyte complexes. These studies shed light on the chemical groups involved in the analyte-selector interaction and provided useful information for a wider application of these cyclopeptides in the separation of other drug enantiomers.

Chiral Dynamics 2006

NASA Astrophysics Data System (ADS)

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

2007-10-01

of singular potentials and power counting / M.P. Valderrrama. The challenge of calculating Baryon-Baryon scattering from lattice QCD / S.R. Beane. Precise absolute np scattering cross section and the charged [Pie symbol] NN coupling constant / S. E. Vigdor. Probing hadronic parity violation using few nucleon systems / S.A. Page. Extracting the neutron-neutron scattering length from neutron-deuteron breakup / C.R. Howell. Extraction of [equationl] from [Pie symbol]-d --> [equation] / A. Grudestig. The three- and four-body system with large scattering length / L. Platter. 3N and 4N systems and the Ay puzzle / T. Clegg. Recent progress in nuclear lattice simulations with effective field theory / D. Lee. Few-body studies at KVI / J.G. Messchendorp. Results of three nucleon experiments from RIKEN / K. Sekiguchi. A new opportunity to measure the total photoabsorption cross section of helium / P. T. Debevec. Three-body photodisintegration of 3He with double polarizations / X. Zong. Large two-pion exchange contributions to the pp --> pp[Pie symbol]0 reaction / F. Myhrer. Towards a systematic theory of nuclear forces / E. Epelbaum. Ab initio calculations of eletromagnetic reactions in light nuclei / W. Leidemann. Electron scattering from a polarized deuterium target at BLAST / R. Fatemi. Neutron-neutron scattering length from the reaction [equation] / V. Lensky. Renormalization group analysis of nuclear current operators / S.X. Nakamura. Recent results and future plans at MAX-LAB / K.G. Fissum. Nucleon polarizabilities from deutron compton scattering, and its lessons for chiral power counting / H. W. Grie hammer. Compton scattering on HE-3 / D. Choudhury -- pt. D. Hadron structure and Meson-Baryon interactions. Summary of the working group on Hadron structure and Meson-Baryon interactions / G. Feldman and T.R. Hemmert. Finite volume effects: lattice meets CHPT / G. Schierholz. Lattice discretization errors in chiral effective field theories / B.C. Tiburzi. SU(3)-breaking

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)

Chiral acidic amino acids induce chiral hierarchical structure in calcium carbonate

PubMed Central

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

2017-01-01

Chirality is ubiquitous in biology, including in biomineralization, where it is found in many hardened structures of invertebrate marine and terrestrial organisms (for example, spiralling gastropod shells). Here we show that chiral, hierarchically organized architectures for calcium carbonate (vaterite) can be controlled simply by adding chiral acidic amino acids (Asp and Glu). Chiral, vaterite toroidal suprastructure having a ‘right-handed' (counterclockwise) spiralling morphology is induced by L-enantiomers of Asp and Glu, whereas ‘left-handed' (clockwise) morphology is induced by D-enantiomers, and sequentially switching between amino-acid enantiomers causes a switch in chirality. Nanoparticle tilting after binding of chiral amino acids is proposed as a chiral growth mechanism, where a ‘mother' subunit nanoparticle spawns a slightly tilted, consequential ‘daughter' nanoparticle, which by amplification over various length scales creates oriented mineral platelets and chiral vaterite suprastructures. These findings suggest a molecular mechanism for how biomineralization-related enantiomers might exert hierarchical control to form extended chiral suprastructures. PMID:28406143

Tailoring the chirality of light emission with spherical Si-based antennas.

PubMed

Zambrana-Puyalto, Xavier; Bonod, Nicolas

2016-05-21

Chirality of light is of fundamental importance in several enabling technologies with growing applications in life sciences, chemistry and photodetection. Recently, some attention has been focused on chiral quantum emitters. Consequently, optical antennas which are able to tailor the chirality of light emission are needed. Spherical nanoresonators such as colloids are of particular interest to design optical antennas since they can be synthesized at a large scale and they exhibit good optical properties. Here, we show that these colloids can be used to tailor the chirality of a chiral emitter. To this purpose, we derive an analytic formalism to model the interaction between a chiral emitter and a spherical resonator. We then compare the performances of metallic and dielectric spherical antennas to tailor the chirality of light emission. It is seen that, due to their strong electric dipolar response, metallic spherical nanoparticles spoil the chirality of light emission by yielding achiral fields. In contrast, thanks to the combined excitation of electric and magnetic modes, dielectric Si-based particles feature the ability to inhibit or to boost the chirality of light emission. Finally, it is shown that dual modes in dielectric antennas preserve the chirality of light emission.

2, 84, 30, 993, 560, 15456, 11962, 261485, . . .: higher dimension operators in the SM EFT

DOE PAGES

Henning, Brian; Lu, Xiaochuan; Melia, Tom; ...

2017-08-04

In a companion paper, we show that operator bases for general effective field theories are controlled by the conformal algebra. Equations of motion and integration by parts identities can be systematically treated by organizing operators into irreducible representations of the conformal group. In the present work, we use this result to study the standard model effective field theory (SM EFT), determining the content and number of higher dimension operators up to dimension 12, for an arbitrary number of fermion generations. We find additional operators to those that have appeared in the literature at dimension 7 (specifically in the case ofmore » more than one fermion generation) and at dimension 8. (The title sequence is the total number of independent operators in the SM EFT with one fermion generation, including hermitian conjugates, ordered in mass dimension, starting at dimension 5.)« less

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.

Semilocal momentum-space regularized chiral two-nucleon potentials up to fifth order

NASA Astrophysics Data System (ADS)

Reinert, P.; Krebs, H.; Epelbaum, E.

2018-05-01

We introduce new semilocal two-nucleon potentials up to fifth order in the chiral expansion. We employ a simple regularization approach for the pion exchange contributions which i) maintains the long-range part of the interaction, ii) is implemented in momentum space and iii) can be straightforwardly applied to regularize many-body forces and current operators. We discuss in detail the two-nucleon contact interactions at fourth order and demonstrate that three terms out of fifteen used in previous calculations can be eliminated via suitably chosen unitary transformations. The removal of the redundant contact terms results in a drastic simplification of the fits to scattering data and leads to interactions which are much softer ( i.e., more perturbative) than our recent semilocal coordinate-space regularized potentials. Using the pion-nucleon low-energy constants from matching pion-nucleon Roy-Steiner equations to chiral perturbation theory, we perform a comprehensive analysis of nucleon-nucleon scattering and the deuteron properties up to fifth chiral order and study the impact of the leading F-wave two-nucleon contact interactions which appear at sixth order. The resulting chiral potentials at fifth order lead to an outstanding description of the proton-proton and neutron-proton scattering data from the self-consistent Granada-2013 database below the pion production threshold, which is significantly better than for any other chiral potential. For the first time, the chiral potentials match in precision and even outperform the available high-precision phenomenological potentials, while the number of adjustable parameters is, at the same time, reduced by about ˜ 40%. Last but not least, we perform a detailed error analysis and, in particular, quantify for the first time the statistical uncertainties of the fourth- and the considered sixth-order contact interactions.

NASA Ames Contributes to Orion / EFT-1 Test Flight (Reporter Pkg)

NASA Image and Video Library

2014-12-03

NASA's Orion spacecraft is built to take humans farther than they've ever gone before. Orion will serve as the exploration vehicle that will carry the crew to space, provide emergency abort capability, sustain the crew during the space travel, and provide safe re-entry from deep space return velocities. NASA's Ames Research Center played a critical role in the development and preparation for the flight test designated Exploration Flight Test 1, or EFT-1.

Delta Mariner arrival with EFT-1 Booster

NASA Image and Video Library

2014-03-03

CAPE CANAVERAL, Fla. – The United Launch Alliance barge Delta Mariner glides past the jetties as it enters Port Canaveral in Florida. The barge is carrying two of the booster stages for the Delta IV Heavy rocket slated for Orion's Exploration Flight Test-1, or EFT-1. Orion is the exploration spacecraft designed to carry astronauts to destinations not yet explored by humans. It will have emergency abort capability, sustain the crew during space travel and provide safe re-entry from deep-space return velocities. The first unpiloted test flight of Orion is scheduled to launch in September 2014 atop a Delta IV Heavy rocket and in 2017 on NASA’s Space Launch System rocket. For more information, visit www.nasa.gov/orion. Photo credit: NASA/Frankie Martin

Determining the orientation of a chiral substrate using full-hemisphere angle-resolved photoelectron spectroscopy.

PubMed

Tadich, A; Riley, J; Thomsen, L; Cowie, B C C; Gladys, M J

2011-10-21

Chiral interfaces and substrates are of increasing importance in the field of enantioselective chemistry. To fully understand the enantiospecific interactions between chiral adsorbate molecules and the chiral substrate, it is vital that the chiral orientation of the substrate is known. In this Letter we demonstrate that full-hemisphere angle-resolved photoemission permits straightforward identification of the orientation of a chiral surface. The technique can be applied to any solid state system for which photoemission measurements are possible. © 2011 American Physical Society

First-order chiral to non-chiral transition in the angular dependence of the upper critical induction of the Scharnberg-Klemm p-wave pair state

NASA Astrophysics Data System (ADS)

Klemm, Richard; Zhang, Jingchuan; Lorscher, Christopher; Gu, Qiang

2014-03-01

We calculate the temperature T and angular (θ , ϕ) dependence of the upper critical induction Bc 2(θ , ϕ , T) for parallel-spin superconductors with an axially symmetric p-wave pairing interaction pinned to the lattice and a dominant ellipsoidal Fermi surface (FS). When both parallel-spin states are allowed, the chiral Scharnberg-Klemm state Bc 2(θ , ϕ , T) exceeds that of the chiral Anderson-Brinkman-Morel state for all FS anisotropies, and exhibits a kink at θ =θ*(T , ϕ) , indicative of a first-order transition from its chiral, nodal-direction behavior to its non-chiral, antinodal-direction behavior. Potential applicability to Sr2RuO4, UCoGe, and topological superconductors is discussed.

Can a Linear Sigma Model Describe Walking Gauge Theories at Low Energies?

NASA Astrophysics Data System (ADS)

Gasbarro, Andrew

2018-03-01

In recent years, many investigations of confining Yang Mills gauge theories near the edge of the conformal window have been carried out using lattice techniques. These studies have revealed that the spectrum of hadrons in nearly conformal ("walking") gauge theories differs significantly from the QCD spectrum. In particular, a light singlet scalar appears in the spectrum which is nearly degenerate with the PNGBs at the lightest currently accessible quark masses. This state is a viable candidate for a composite Higgs boson. Presently, an acceptable effective field theory (EFT) description of the light states in walking theories has not been established. Such an EFT would be useful for performing chiral extrapolations of lattice data and for serving as a bridge between lattice calculations and phenomenology. It has been shown that the chiral Lagrangian fails to describe the IR dynamics of a theory near the edge of the conformal window. Here we assess a linear sigma model as an alternate EFT description by performing explicit chiral fits to lattice data. In a combined fit to the Goldstone (pion) mass and decay constant, a tree level linear sigma model has a Χ2/d.o.f. = 0.5 compared to Χ2/d.o.f. = 29.6 from fitting nextto-leading order chiral perturbation theory. When the 0++ (σ) mass is included in the fit, Χ2/d.o.f. = 4.9. We remark on future directions for providing better fits to the σ mass.

Estimating Orion Heat Shield Failure Due To Ablator Cracking During The EFT-1 Mission

NASA Technical Reports Server (NTRS)

Vander Kam, Jeremy C.; Gage, Peter

2016-01-01

The Orion EFT-1 heatshield suffered from two major certification challenges: First, the mechanical properties used in design were not evident in the flight hardware and second, the flight article itself cracked during fabrication. The combination of these events motivated the Orion Program to pursue an engineering-level Probabilistic Risk Assessment (PRA) as part of heatshield certification rationale. The PRA provided loss of Mission (LOM) likelihoods considering the probability of a crack occurring during the mission and the likelihood of subsequent structure over-temperature. The methods and input data for the PRA are presented along with a discussion of the test data used to anchor the results. The Orion program accepted an EFT-1 Loss of Vehicle (LOV) risk of 1-in-160,000 due to in-mission Avcoat cracking based on the results of this analysis. Conservatisms in the result, along with future considerations for Exploration Missions (EM) are also addressed.

Chiral d -wave superconductivity in a triangular surface lattice mediated by long-range interaction

NASA Astrophysics Data System (ADS)

Cao, Xiaodong; Ayral, Thomas; Zhong, Zhicheng; Parcollet, Olivier; Manske, Dirk; Hansmann, Philipp

2018-04-01

Adatom systems on the Si(111) surface have recently attracted an increasing attention as strongly correlated systems with a rich phase diagram. We study these materials by a single band model on the triangular lattice, including 1 /r long-range interaction. Employing the recently proposed TRILEX method, we find an unconventional superconducting phase of chiral d -wave symmetry in hole-doped systems. Contrary to usual scenarios where charge and spin fluctuations are seen to compete, here the superconductivity is driven simultaneously by both charge and spin fluctuations and crucially relies on the presence of the long-range tail of the interaction. We provide an analysis of the relevant collective bosonic modes and predict how a cumulative charge and spin paring mechanism leads to superconductivity in doped silicon adatom materials.

Chiral Spin Order in Kondo-Heisenberg systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsvelik, A. M.; Yevtushenko, O. M.

We demonstrate that Kondo-Heisenberg systems, consisting of itinerant electrons and localized magnetic moments (Kondo impurities), can be used as a principally new platform to realize scalar chiral spin order. The underlying physics is governed by a competition of the Ruderman-Kittel- Kosuya-Yosida (RKKY) indirect exchange interaction between the local moments with the direct Heisenberg one. When the direct exchange is weak and RKKY dominates the isotropic system is in the disordered phase. A moderately large direct exchange leads to an Ising-type phase transition to the phase with chiral spin order. Our nding paves the way towards pioneering experimental realizations of themore » chiral spin liquid in low dimensional systems with spontaneously broken time reversal symmetry.« less

Chiral Spin Order in Kondo-Heisenberg systems

DOE PAGES

Tsvelik, A. M.; Yevtushenko, O. M.

2017-12-15

We demonstrate that Kondo-Heisenberg systems, consisting of itinerant electrons and localized magnetic moments (Kondo impurities), can be used as a principally new platform to realize scalar chiral spin order. The underlying physics is governed by a competition of the Ruderman-Kittel- Kosuya-Yosida (RKKY) indirect exchange interaction between the local moments with the direct Heisenberg one. When the direct exchange is weak and RKKY dominates the isotropic system is in the disordered phase. A moderately large direct exchange leads to an Ising-type phase transition to the phase with chiral spin order. Our nding paves the way towards pioneering experimental realizations of themore » chiral spin liquid in low dimensional systems with spontaneously broken time reversal symmetry.« less

Experimental Evidence of Chiral Ferrimagnetism in Amorphous GdCo Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Streubel, Robert; Lambert, Charles-Henri; Kent, Noah

Inversion symmetry breaking has become a vital research area in modern magnetism with phenomena including the Rashba effect, spin Hall effect, and the Dzyaloshinskii-Moriya interaction (DMI)-a vector spin exchange. The latter one may stabilize chiral spin textures with topologically nontrivial properties, such as Skyrmions. So far, chiral spin textures have mainly been studied in helimagnets and thin ferromagnets with heavy-element capping. Here, the concept of chirality driven by interfacial DMI is generalized to complex multicomponent systems and demonstrated on the example of chiral ferrimagnetism in amorphous GdCo films. Utilizing Lorentz microscopy and X-ray magnetic circular dichroism spectroscopy, and tailoring thickness,more » capping, and rare-earth composition, reveal that 2 nm thick GdCo films preserve ferrimagnetism and stabilize chiral domain walls. Finally, the type of chiral domain walls depends on the rare-earth composition/saturation magnetization, enabling a possible temperature control of the intrinsic properties of ferrimagnetic domain walls.« less

Experimental Evidence of Chiral Ferrimagnetism in Amorphous GdCo Films

DOE PAGES

Streubel, Robert; Lambert, Charles-Henri; Kent, Noah; ...

2018-05-23

Inversion symmetry breaking has become a vital research area in modern magnetism with phenomena including the Rashba effect, spin Hall effect, and the Dzyaloshinskii-Moriya interaction (DMI)-a vector spin exchange. The latter one may stabilize chiral spin textures with topologically nontrivial properties, such as Skyrmions. So far, chiral spin textures have mainly been studied in helimagnets and thin ferromagnets with heavy-element capping. Here, the concept of chirality driven by interfacial DMI is generalized to complex multicomponent systems and demonstrated on the example of chiral ferrimagnetism in amorphous GdCo films. Utilizing Lorentz microscopy and X-ray magnetic circular dichroism spectroscopy, and tailoring thickness,more » capping, and rare-earth composition, reveal that 2 nm thick GdCo films preserve ferrimagnetism and stabilize chiral domain walls. Finally, the type of chiral domain walls depends on the rare-earth composition/saturation magnetization, enabling a possible temperature control of the intrinsic properties of ferrimagnetic domain walls.« less

Imaging chiral symmetry breaking from Kekule bond order in graphene

DOE PAGES

Gutiérrez, Christopher; Kim, Cheol -Joo; Brown, Lola; ...

2016-05-23

Chirality—or ‘handedness’—is a symmetry property crucial to fields as diverse as biology, chemistry and high-energy physics. In graphene, chiral symmetry emerges naturally as a consequence of the carbon honeycomb lattice. This symmetry can be broken by interactions that couple electrons with opposite momenta in graphene. Here we directly visualize the formation of Kekulé bond order, one such phase of broken chiral symmetry, in an ultraflat graphene sheet grown epitaxially on a copper substrate. We show that its origin lies in the interactions between individual vacancies in the copper substrate that are mediated electronically by the graphene. We show that thismore » interaction causes the bonds in graphene to distort, creating a phase with broken chiral symmetry. Furthermore, the Kekulé ordering is robust at ambient temperature and atmospheric conditions, indicating that intercalated atoms may be harnessed to drive graphene and other two-dimensional materials towards electronically desirable and exotic collective phases.« less

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

PubMed

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

2018-05-11

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

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

In pursuit of photo-induced magnetic and chiral microscopy

NASA Astrophysics Data System (ADS)

Zeng, Jinwei; Kamandi, Mohammad; Darvishzadeh-Varcheie, Mahsa; Albooyeh, Mohammad; Veysi, Mehdi; Guclu, Caner; Hanifeh, Mina; Rajaei, Mohsen; Potma, Eric O.; Wickramasinghe, H. Kumar; Capolino, Filippo

2018-06-01

Light-matter interactions enable the perception of specimen properties such as its shape and dimensions by measuring the subtle differences carried by an illuminating beam after interacting with the sample. However, major obstacles arise when the relevant properties of the specimen are weakly coupled to the incident beam, for example when measuring optical magnetism and chirality. To address this challenge we propose the idea of detecting such weakly-coupled properties of matter through the photo-induced force, aiming at developing photo-induced magnetic or chiral force microscopy. Here we review our pursuit consisting of the following steps: (1) Development of a theoretical blueprint of a magnetic nanoprobe to detect a magnetic dipole oscillating at an optical frequency when illuminated by an azimuthally polarized beam via the photo-induced magnetic force; (2) Conducting an experimental study using an azimuthally polarized beam to probe the near fields and axial magnetism of a Si disk magnetic nanoprobe, based on photo-induced force microscopy; (3) Extending the concept of force microscopy to probe chirality at the nanoscale, enabling enantiomeric detection of chiral molecules. Finally, we discuss difficulties and how they could be overcome, as well as our plans for future work. Invited Paper

77 FR 22067 - Proposed Collection of Information: Trace Request for Electronic Funds Transfer (EFT) Payment...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-04-12

... Electronic Funds Transfer (EFT) Payment; and Trace Request Direct Deposit AGENCY: Financial Management... collection. By this notice, the Financial Management Service solicits comments concerning forms FMS-150.1... comments to Financial Management Service, 3700 East West Highway, Records and Information Management Branch...

Electric line source illumination of a chiral cylinder placed in another chiral background medium

NASA Astrophysics Data System (ADS)

Aslam, M.; Saleem, A.; Awan, Z. A.

2018-05-01

An electric line source illumination of a chiral cylinder embedded in a chiral background medium is considered. The field expressions inside and outside of a chiral cylinder have been derived using the wave field decomposition approach. The effects of various chiral cylinders, chiral background media and source locations upon the scattering gain pattern have been investigated. It is observed that the chiral background reduces the backward scattering gain as compared to the free space background for a dielectric cylinder. It is also studied that by moving a line source away from a cylinder reduces the backward scattering gain for a chiral cylinder placed in a chiral background under some specific conditions. A unique phenomenon of reduced scattering gain has been observed at a specific observation angle for a chiral cylinder placed in a chiral background having an electric line source location of unity free space wavelength. An isotropic scattering gain pattern is observed for a chiral nihility background provided that if cylinder is chiral or chiral nihility type. It is also observed that this isotropic behaviour is independent of background and cylinder chirality.

Deracemization of bilirubin as the marker of the chirality of micellar aggregates.

PubMed

Sorrenti, Alessandro; Altieri, Barbara; Ceccacci, Francesca; Di Profio, Pietro; Germani, Raimondo; Giansanti, Luisa; Savelli, Gianfranco; Mancini, Giovanna

2012-01-01

The deracemization of bilirubin in micellar aggregates of structurally correlated chiral surfactants was studied by circular dichroism experiments and exploited as the marker of the expression of chirality of the aggregates. The obtained results suggest that the hydrophobic interactions control the transfer of chirality from the monomers to the aggregates, and that different regions of the same aggregate might feature opposite enantiorecognition capabilities. Copyright © 2011 Wiley-Liss, Inc.

Stoichiometry-Controlled Inversion of Supramolecular Chirality in Nanostructures Co-assembled with Bipyridines.

PubMed

Wang, Fang; Feng, Chuan-Liang

2018-02-01

To control supramolecular chirality of the co-assembled nanostructures, one of the remaining issues is how stoichiometry of the different molecules involved in co-assembly influence chiral transformation. Through co-assembly of achiral 1,4-bis(pyrid-4-yl)benzene and chiral phenylalanine-glycine derivative hydrogelators, stoichiometry is found to be an effective tool for controlling supramolecular chirality inversion processes. This inversion is mainly mediated by a delicate balance between intermolecular hydrogen bonding interactions and π-π stacking of the two components, which may subtly change the stacking of the molecules, in turn, the self-assembled nanostructures. This study exemplifies a simplistic way to invert the handedness of chiral nanostructures and provide fundamental understanding of the inherent principles of supramolecular chirality. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anion-π Catalysts with Axial Chirality.

PubMed

Wang, Chao; Matile, Stefan

2017-09-04

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

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.

Chiral magnetic effect in lattice QCD with a chiral chemical potential.

PubMed

Yamamoto, Arata

2011-07-15

We perform a first lattice QCD simulation including a two-flavor dynamical fermion with a chiral chemical potential. Because the chiral chemical potential gives rise to no sign problem, we can exactly analyze a chirally imbalanced QCD matter by Monte Carlo simulation. By applying an external magnetic field to this system, we obtain a finite induced current along the magnetic field, which corresponds to the chiral magnetic effect. The obtained induced current is proportional to the magnetic field and to the chiral chemical potential, which is consistent with an analytical prediction.

Spin-orbit beams for optical chirality measurement

NASA Astrophysics Data System (ADS)

Samlan, C. T.; Suna, Rashmi Ranjan; Naik, Dinesh N.; Viswanathan, Nirmal K.

2018-01-01

Accurate measurement of chirality is essential for the advancement of natural and pharmaceutical sciences. We report here a method to measure chirality using non-separable states of light with geometric phase-gradient in the circular polarization basis, which we refer to as spin-orbit beams. A modified polarization Sagnac interferometer is used to generate spin-orbit beams wherein the spin and orbital angular momentum of the input Gaussian beam are coupled. The out-of-phase interference between counter-propagating Gaussian beams with orthogonal spin states and lateral-shear or/and linear-phase difference between them results in spin-orbit beams with linear and azimuthal phase gradient. The spin-orbit beams interact efficiently with the chiral medium, inducing a measurable change in the center-of-mass of the beam, using the polarization rotation angle and hence the chirality of the medium are accurately calculated. Tunable dynamic range of measurement and flexibility to introduce large values of orbital angular momentum for the spin-orbit beam, to improve the measurement sensitivity, highlight the techniques' versatility.

Chiral higher spin theories and self-duality

NASA Astrophysics Data System (ADS)

Ponomarev, Dmitry

2017-12-01

We study recently proposed chiral higher spin theories — cubic theories of interacting massless higher spin fields in four-dimensional flat space. We show that they are naturally associated with gauge algebras, which manifest themselves in several related ways. Firstly, the chiral higher spin equations of motion can be reformulated as the self-dual Yang-Mills equations with the associated gauge algebras instead of the usual colour gauge algebra. We also demonstrate that the chiral higher spin field equations, similarly to the self-dual Yang-Mills equations, feature an infinite algebra of hidden symmetries, which ensures their integrability. Secondly, we show that off-shell amplitudes in chiral higher spin theories satisfy the generalised BCJ relations with the usual colour structure constants replaced by the structure constants of higher spin gauge algebras. We also propose generalised double copy procedures featuring higher spin theory amplitudes. Finally, using the light-cone deformation procedure we prove that the structure of the Lagrangian that leads to all these properties is universal and follows from Lorentz invariance.

The interplay of covalency, hydrogen bonding, and dispersion leads to a long range chiral network: The example of 2-butanol

NASA Astrophysics Data System (ADS)

Liriano, Melissa L.; Carrasco, Javier; Lewis, Emily A.; Murphy, Colin J.; Lawton, Timothy J.; Marcinkowski, Matthew D.; Therrien, Andrew J.; Michaelides, Angelos; Sykes, E. Charles H.

2016-03-01

The assembly of complex structures in nature is driven by an interplay between several intermolecular interactions, from strong covalent bonds to weaker dispersion forces. Understanding and ultimately controlling the self-assembly of materials requires extensive study of how these forces drive local nanoscale interactions and how larger structures evolve. Surface-based self-assembly is particularly amenable to modeling and measuring these interactions in well-defined systems. This study focuses on 2-butanol, the simplest aliphatic chiral alcohol. 2-butanol has recently been shown to have interesting properties as a chiral modifier of surface chemistry; however, its mode of action is not fully understood and a microscopic understanding of the role non-covalent interactions play in its adsorption and assembly on surfaces is lacking. In order to probe its surface properties, we employed high-resolution scanning tunneling microscopy and density functional theory (DFT) simulations. We found a surprisingly rich degree of enantiospecific adsorption, association, chiral cluster growth and ultimately long range, highly ordered chiral templating. Firstly, the chiral molecules acquire a second chiral center when adsorbed to the surface via dative bonding of one of the oxygen atom lone pairs. This interaction is controlled via the molecule's intrinsic chiral center leading to monomers of like chirality, at both chiral centers, adsorbed on the surface. The monomers then associate into tetramers via a cyclical network of hydrogen bonds with an opposite chirality at the oxygen atom. The evolution of these square units is surprising given that the underlying surface has a hexagonal symmetry. Our DFT calculations, however, reveal that the tetramers are stable entities that are able to associate with each other by weaker van der Waals interactions and tessellate in an extended square network. This network of homochiral square pores grows to cover the whole Au(111) surface. Our data

The interplay of covalency, hydrogen bonding, and dispersion leads to a long range chiral network: The example of 2-butanol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liriano, Melissa L.; Lewis, Emily A.; Murphy, Colin J.

The assembly of complex structures in nature is driven by an interplay between several intermolecular interactions, from strong covalent bonds to weaker dispersion forces. Understanding and ultimately controlling the self-assembly of materials requires extensive study of how these forces drive local nanoscale interactions and how larger structures evolve. Surface-based self-assembly is particularly amenable to modeling and measuring these interactions in well-defined systems. This study focuses on 2-butanol, the simplest aliphatic chiral alcohol. 2-butanol has recently been shown to have interesting properties as a chiral modifier of surface chemistry; however, its mode of action is not fully understood and a microscopicmore » understanding of the role non-covalent interactions play in its adsorption and assembly on surfaces is lacking. In order to probe its surface properties, we employed high-resolution scanning tunneling microscopy and density functional theory (DFT) simulations. We found a surprisingly rich degree of enantiospecific adsorption, association, chiral cluster growth and ultimately long range, highly ordered chiral templating. Firstly, the chiral molecules acquire a second chiral center when adsorbed to the surface via dative bonding of one of the oxygen atom lone pairs. This interaction is controlled via the molecule’s intrinsic chiral center leading to monomers of like chirality, at both chiral centers, adsorbed on the surface. The monomers then associate into tetramers via a cyclical network of hydrogen bonds with an opposite chirality at the oxygen atom. The evolution of these square units is surprising given that the underlying surface has a hexagonal symmetry. Our DFT calculations, however, reveal that the tetramers are stable entities that are able to associate with each other by weaker van der Waals interactions and tessellate in an extended square network. This network of homochiral square pores grows to cover the whole Au(111) surface

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

PubMed

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.

Chiral Polymers.

DTIC Science & Technology

1984-10-01

regardless of the method of polymerization. The styrene-bead copolymers were packed in HPLC columns, but none were especiall, effective in separating...enantiomers in a racemic mixture. The chiral butyrolactone polymer was coated on silica, but this material did not effect resolution of racemic mixtures in an...been effected utilizing chiral oxazolines3 prompted the initial efforts to synthesize various chiral 2-vinyl- oxazoline monomers for incorporation

Wilson loops and chiral correlators on squashed spheres

NASA Astrophysics Data System (ADS)

Fucito, F.; Morales, J. F.; Poghossian, R.

2015-11-01

We study chiral deformations of N=2 and N=4 supersymmetric gauge theories obtained by turning on τ J tr Φ J interactions with Φ the N=2 superfield. Using localization, we compute the deformed gauge theory partition function Z(overrightarrow{τ}|q) and the expectation value of circular Wilson loops W on a squashed four-sphere. In the case of the deformed {N}=4 theory, exact formulas for Z and W are derived in terms of an underlying U( N) interacting matrix model replacing the free Gaussian model describing the {N}=4 theory. Using the AGT correspondence, the τ J -deformations are related to the insertions of commuting integrals of motion in the four-point CFT correlator and chiral correlators are expressed as τ-derivatives of the gauge theory partition function on a finite Ω-background. In the so called Nekrasov-Shatashvili limit, the entire ring of chiral relations is extracted from the ɛ-deformed Seiberg-Witten curve. As a byproduct of our analysis we show that SU(2) gauge theories on rational Ω-backgrounds are dual to CFT minimal models.

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.)

Chiral quantum optics.

PubMed

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

2017-01-25

Advanced photonic nanostructures are currently revolutionizing the optics and photonics that underpin applications ranging from light technology to quantum-information processing. The strong light confinement in these structures can lock the local polarization of the light to its propagation direction, leading to propagation-direction-dependent emission, scattering and absorption of photons by quantum emitters. The possibility of such a propagation-direction-dependent, or chiral, light-matter interaction is not accounted for in standard quantum optics and its recent discovery brought about the research field of chiral quantum optics. The latter offers fundamentally new functionalities and applications: it enables the assembly of non-reciprocal single-photon devices that can be operated in a quantum superposition of two or more of their operational states and the realization of deterministic spin-photon interfaces. Moreover, engineered directional photonic reservoirs could lead to the development of complex quantum networks that, for example, could simulate novel classes of quantum many-body systems.

Attosecond-resolved photoionization of chiral molecules.

PubMed

Beaulieu, S; Comby, A; Clergerie, A; Caillat, J; Descamps, D; Dudovich, N; Fabre, B; Géneaux, R; Légaré, F; Petit, S; Pons, B; Porat, G; Ruchon, T; Taïeb, R; Blanchet, V; Mairesse, Y

2017-12-08

Chiral light-matter interactions have been investigated for two centuries, leading to the discovery of many chiroptical processes used for discrimination of enantiomers. Whereas most chiroptical effects result from a response of bound electrons, photoionization can produce much stronger chiral signals that manifest as asymmetries in the angular distribution of the photoelectrons along the light-propagation axis. We implemented self-referenced attosecond photoelectron interferometry to measure the temporal profile of the forward and backward electron wave packets emitted upon photoionization of camphor by circularly polarized laser pulses. We measured a delay between electrons ejected forward and backward, which depends on the ejection angle and reaches 24 attoseconds. The asymmetric temporal shape of electron wave packets emitted through an autoionizing state further reveals the chiral character of strongly correlated electronic dynamics. Copyright © 2017 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

Assembly of mesoscale helices with near-unity enantiomeric excess and light-matter interactions for chiral semiconductors.

PubMed

Feng, Wenchun; Kim, Ji-Young; Wang, Xinzhi; Calcaterra, Heather A; Qu, Zhibei; Meshi, Louisa; Kotov, Nicholas A

2017-03-01

Semiconductors with chiral geometries at the nanoscale and mesoscale provide a rich materials platform for polarization optics, photocatalysis, and biomimetics. Unlike metallic and organic optical materials, the relationship between the geometry of chiral semiconductors and their chiroptical properties remains, however, vague. Homochiral ensembles of semiconductor helices with defined geometries open the road to understanding complex relationships between geometrical parameters and chiroptical properties of semiconductor materials. We show that semiconductor helices can be prepared with an absolute yield of ca 0.1% and an enantiomeric excess (e.e.) of 98% or above from cysteine-stabilized cadmium telluride nanoparticles (CdTe NPs) dispersed in methanol. This high e.e. for a spontaneously occurring chemical process is attributed to chiral self-sorting based on the thermodynamic preference of NPs to assemble with those of the same handedness. The dispersions of homochiral self-assembled helices display broadband visible and near-infrared (Vis-NIR) polarization rotation with anisotropy ( g ) factors approaching 0.01. Calculated circular dichroism (CD) spectra accurately reproduced experimental CD spectra and gave experimentally validated spectral predictions for different geometrical parameters enabling de novo design of chiroptical semiconductor materials. Unlike metallic, ceramic, and polymeric helices that serve predominantly as scatterers, chiroptical properties of semiconductor helices have nearly equal contribution of light absorption and scattering, which is essential for device-oriented, field-driven light modulation. Deconstruction of a helix into a series of nanorods provides a simple model for the light-matter interaction and chiroptical activity of helices. This study creates a framework for further development of polarization-based optics toward biomedical applications, telecommunications, and hyperspectral imaging.

Chiral crossover transition in a finite volume

NASA Astrophysics Data System (ADS)

Shi, Chao; Jia, Wenbao; Sun, An; Zhang, Liping; Zong, Hongshi

2018-02-01

Finite volume effects on the chiral crossover transition of strong interactions at finite temperature are studied by solving the quark gap equation within a cubic volume of finite size L. With the anti-periodic boundary condition, our calculation shows the chiral quark condensate, which characterizes the strength of dynamical chiral symmetry breaking, decreases as L decreases below 2.5 fm. We further study the finite volume effects on the pseudo-transition temperature {T}{{c}} of the crossover, showing a significant decrease in {T}{{c}} as L decreases below 3 fm. Supported by National Natural Science Foundation of China (11475085, 11535005, 11690030, 51405027), the Fundamental Research Funds for the Central Universities (020414380074), China Postdoctoral Science Foundation (2016M591808) and Open Research Foundation of State Key Lab. of Digital Manufacturing Equipment & Technology in Huazhong University of Science & Technology (DMETKF2015015)

Magnetic fields and chiral asymmetry in the early hot universe

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sydorenko, Maksym; Shtanov, Yuri; Tomalak, Oleksandr, E-mail: maxsydorenko@gmail.com, E-mail: tomalak@uni-mainz.de, E-mail: shtanov@bitp.kiev.ua

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 andmore » 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.« less

Origin of Stereodivergence in Cooperative Asymmetric Catalysis with Simultaneous Involvement of Two Chiral Catalysts.

PubMed

Bhaskararao, Bangaru; Sunoj, Raghavan B

2015-12-23

Accomplishing high diastereo- and enantioselectivities simultaneously is a persistent challenge in asymmetric catalysis. The use of two chiral catalysts in one-pot conditions might offer new avenues to this end. Chirality transfer from a catalyst to product gets increasingly complex due to potential chiral match-mismatch issues. The origin of high enantio- and diastereoselectivities in the reaction between a racemic aldehyde and an allyl alcohol, catalyzed by using axially chiral iridium phosphoramidites PR/S-Ir and cinchona amine is established through transition-state modeling. The multipoint contact analysis of the stereocontrolling transition state revealed how the stereodivergence could be achieved by inverting the configuration of the chiral catalysts that are involved in the activation of the reacting partners. While the enantiocontrol is identified as being decided in the generation of PR/S-Ir-π-allyl intermediate from the allyl alcohol, the diastereocontrol arises due to the differential stabilizations in the C-C bond formation transition states. The analysis of the weak interactions in the transition states responsible for chiral induction revealed that the geometric disposition of the quinoline ring at the C8 chiral carbon of cinchona-enamine plays an anchoring role. The quinolone ring is noted as participating in a π-stacking interaction with the phenyl ring of the Ir-π-allyl moiety in the case of PR with the (8R,9R)-cinchona catalyst combination, whereas a series of C-H···π interactions is identified as vital to the relative stabilization of the stereocontrolling transition states when PR is used with (8S,9S)-cinchona.

Mixing and demixing of binary mixtures of polar chiral active particles.

PubMed

Ai, Bao-Quan; Shao, Zhi-Gang; Zhong, Wei-Rong

2018-05-17

We study a binary mixture of polar chiral (counterclockwise or clockwise) active particles in a two-dimensional box with periodic boundary conditions. Besides the excluded volume interactions between particles, the particles are also subjected to the polar velocity alignment. From the extensive Brownian dynamics simulations, it is found that the particle configuration (mixing or demixing) is determined by the competition between the chirality difference and the polar velocity alignment. When the chirality difference competes with the polar velocity alignment, the clockwise particles aggregate in one cluster and the counterclockwise particles aggregate in the other cluster; thus, the particles are demixed and can be separated. However, when the chirality difference or the polar velocity alignment is dominant, the particles are mixed. Our findings could be used for the experimental pursuit of the separation of binary mixtures of chiral active particles.

Chiral plasmonics

PubMed Central

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

2017-01-01

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

Enhanced chiral response from the Fabry-Perot cavity coupled meta-surfaces

NASA Astrophysics Data System (ADS)

Yang, Ze-Jian; Hu, De-Jiao; Gao, Fu-Hua; Hou, Yi-Dong

2016-08-01

The circular dichroism (CD) signal of a two-dimensional (2D) chiral meta-surface is usually weak, where the difference between the transmitted (or reflected) right and left circular polarization is barely small. We present a general method to enhance the reflective CD spectrum, by adding a layer of reflective film behind the meta-surface. The light passes through the chiral meta-surface and propagates towards the reflector, where it is reflected back and further interacts with the chiral meta-surface. The light is reflected back and forth between these two layers, forming a Fabry-Perot type resonance, which interacts with the localized surface plasmonic resonance (LSPR) mode and greatly enhances the CD signal of the light wave leaving the meta-surface. We numerically calculate the CD enhancing effect of an L-shaped chiral meta-surface on a gold film in the visible range. Compared with the single layer meta-surface, the L-shaped chiral meta-surface has a CD maximum that is dramatically increased to 1. The analysis of reflection efficiency reveals that our design can be used to realize a reflective circular polarizer. Corresponding mode analysis shows that the huge CD originates from the hybrid mode comprised of FP mode and LSPR. Our results provide a general approach to enhancing the CD signal of a chiral meta-surface and can be used in areas like biosensing, circular polarizer, integrated photonics, etc. Project supported by the National Natural Science Foundation of China (Grant No. 61377054).

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

NASA Astrophysics Data System (ADS)

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

2010-04-01

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

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

DOE PAGES

Kalaydzhyan, Tigran; Murchikova, Elena

2017-03-24

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

Directing the phase behavior of polyelectrolyte complexes using chiral patterned peptides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pacalin, Naomi M.; Leon, Lorraine; Tirrell, Matthew

Polyelectrolyte complexes (PECs) have a broad range of promising applications as soft materials due to their self-assembly and diversity of structure and chemical composition. Peptide polymer PECs are highly biocompatible and biodegradable, making them particularly useful for encapsulation of food additives and flavors, micellar drug delivery, medical and underwater adhesives, fetal membrane patches, and scaffolds for cell growth in tissue engineering. While parameters affecting PEC formation and stability in regards to charge effects are well researched, little is known about the effects of van der Waals interactions, hydrogen bonding, and secondary structure in these materials. Peptide chirality provides a uniquemore » opportunity to manipulate PEC phase to modulate the amount of solid-like (precipitate) or liquid-like (coacervate) character by influencing hydrogen bonding interactions among peptide chains. In previous work, we showed that chiral peptides form solid complexes, while complexes with even one racemic peptide were fluid. This raised the interesting question of how long a homochiral sequence must be to result in solid phase formation. In this work, we designed chiral patterned peptides of polyglutamic acid and polylysine ranging from 50 to 90% L-chiral residues with increasing numbers of sequential L-chiral residues before a chirality change. These polymers were mixed together to form PECs. We observed that 8 or more sequential L-chiral residues are necessary to achieve both the appearance of a precipitate phase and sustained beta-sheets in the complex, as determined by optical imaging and FTIR Spectroscopy. Less homochiral content results in formation of a coacervate phase. Thus, we show that chiral sequence can be used to control the phase transition of PECs. Understanding how to manipulate PEC phase using chiral sequence as presented here may enable tuning of the material properties to achieve the desired mechanical strength for coatings and

Directing the phase behavior of polyelectrolyte complexes using chiral patterned peptides

NASA Astrophysics Data System (ADS)

Pacalin, Naomi M.; Leon, Lorraine; Tirrell, Matthew

2016-10-01

Polyelectrolyte complexes (PECs) have a broad range of promising applications as soft materials due to their self-assembly and diversity of structure and chemical composition. Peptide polymer PECs are highly biocompatible and biodegradable, making them particularly useful for encapsulation of food additives and flavors, micellar drug delivery, medical and underwater adhesives, fetal membrane patches, and scaffolds for cell growth in tissue engineering. While parameters affecting PEC formation and stability in regards to charge effects are well researched, little is known about the effects of van der Waals interactions, hydrogen bonding, and secondary structure in these materials. Peptide chirality provides a unique opportunity to manipulate PEC phase to modulate the amount of solid-like (precipitate) or liquid-like (coacervate) character by influencing hydrogen bonding interactions among peptide chains. In previous work, we showed that chiral peptides form solid complexes, while complexes with even one racemic peptide were fluid. This raised the interesting question of how long a homochiral sequence must be to result in solid phase formation. In this work, we designed chiral patterned peptides of polyglutamic acid and polylysine ranging from 50 to 90% L-chiral residues with increasing numbers of sequential L-chiral residues before a chirality change. These polymers were mixed together to form PECs. We observed that 8 or more sequential L-chiral residues are necessary to achieve both the appearance of a precipitate phase and sustained β-sheets in the complex, as determined by optical imaging and FTIR Spectroscopy. Less homochiral content results in formation of a coacervate phase. Thus, we show that chiral sequence can be used to control the phase transition of PECs. Understanding how to manipulate PEC phase using chiral sequence as presented here may enable tuning of the material properties to achieve the desired mechanical strength for coatings and polymer

Chiral drag force

DOE PAGES

Rajagopal, Krishna; Sadofyev, Andrey V.

2015-10-05

Here, 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 themore » 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

Novel Chiral Magnetic Domain Wall Structure in Fe/Ni/Cu(001) Films

NASA Astrophysics Data System (ADS)

Chen, G.; Zhu, J.; Quesada, A.; Li, J.; N'Diaye, A. T.; Huo, Y.; Ma, T. P.; Chen, Y.; Kwon, H. Y.; Won, C.; Qiu, Z. Q.; Schmid, A. K.; Wu, Y. Z.

2013-04-01

Using spin-polarized low energy electron microscopy, we discovered a new type of domain wall structure in perpendicularly magnetized Fe/Ni bilayers grown epitaxially on Cu(100). Specifically, we observed unexpected Néel-type walls with fixed chirality in the magnetic stripe phase. Furthermore, we find that the chirality of the domain walls is determined by the film growth order with the chirality being right handed in Fe/Ni bilayers and left handed in Ni/Fe bilayers, suggesting that the underlying mechanism is the Dzyaloshinskii-Moriya interaction at the film interfaces. Our observations may open a new route to control chiral spin structures using interfacial engineering in transition metal heterostructures.

Quantum formulation for nanoscale optical and material chirality: symmetry issues, space and time parity, and observables

NASA Astrophysics Data System (ADS)

Andrews, D. L.

2018-03-01

To properly represent the interplay and coupling of optical and material chirality at the photon-molecule or photon-nanoparticle level invites a recognition of quantum facets in the fundamental aspects and mechanisms of light-matter interaction. It is therefore appropriate to cast theory in a general quantum form, one that is applicable to both linear and nonlinear optics as well as various forms of chiroptical interaction including chiral optomechanics. Such a framework, fully accounting for both radiation and matter in quantum terms, facilitates the scrutiny and identification of key issues concerning spatial and temporal parity, scale, dissipation and measurement. Furthermore it fully provides for describing the interactions of structured or twisted light beams with a vortex character, and it leads to the complete identification of symmetry conditions for materials to provide for chiral discrimination. Quantum considerations also lend a distinctive perspective to the very different senses in which other aspects of chirality are recognized in metamaterials. Duly attending to the symmetry principles governing allowed or disallowed forms of chiral discrimination supports an objective appraisal of the experimental possibilities and developing applications.

Self-organization of atoms coupled to a chiral reservoir

NASA Astrophysics Data System (ADS)

Eldredge, Zachary; Solano, Pablo; Chang, Darrick; Gorshkov, Alexey V.

2016-11-01

Tightly confined modes of light, as in optical nanofibers or photonic crystal waveguides, can lead to large optical coupling in atomic systems, which mediates long-range interactions between atoms. These one-dimensional systems can naturally possess couplings that are asymmetric between modes propagating in different directions. Strong long-range interaction among atoms via these modes can drive them to a self-organized periodic distribution. In this paper, we examine the self-organizing behavior of atoms in one dimension coupled to a chiral reservoir. We determine the solution to the equations of motion in different parameter regimes, relative to both the detuning of the pump laser that initializes the atomic dipole-dipole interactions and the degree of reservoir chirality. In addition, we calculate possible experimental signatures such as reflectivity from self-organized atoms and motional sidebands.

Chiral resolution of spin angular momentum in linearly polarized and unpolarized light

PubMed Central

Hernández, R. J.; Mazzulla, A.; Provenzano, C.; Pagliusi, P.; Cipparrone, G.

2015-01-01

Linearly polarized (LP) and unpolarized (UP) light are racemic entities since they can be described as superposition of opposite circularly polarized (CP) components of equal amplitude. As a consequence they do not carry spin angular momentum. Chiral resolution of a racemate, i.e. separation of their chiral components, is usually performed via asymmetric interaction with a chiral entity. In this paper we provide an experimental evidence of the chiral resolution of linearly polarized and unpolarized Gaussian beams through the transfer of spin angular momentum to chiral microparticles. Due to the interplay between linear and angular momentum exchange, basic manipulation tasks, as trapping, spinning or orbiting of micro-objects, can be performed by light with zero helicity. The results might broaden the perspectives for development of miniaturized and cost-effective devices. PMID:26585284

Chiral self-discrimination of the enantiomers of alpha-phenylethylamine derivatives in proton NMR.

PubMed

Huang, Shao-Hua; Bai, Zheng-Wu; Feng, Ji-Wen

2009-05-01

Two types of chiral analytes, the urea and amide derivatives of alpha-phenylethylamine, were prepared. The effect of inter-molecular hydrogen-bonding interaction on self-discrimination of the enantiomers of analytes has been investigated using high-resolution (1)H NMR. It was found that the urea derivatives with double-hydrogen-bonding interaction exhibit not only the stronger hydrogen-bonding interaction but also better self-recognition abilities than the amide derivatives (except for one bearing two NO(2) groups). The present results suggest that double-hydrogen-bonding interaction promotes the self-discrimination ability of the chiral compounds. Copyright (c) 2009 John Wiley & Sons, Ltd.

Characterizing optical chirality

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bliokh, Konstantin Y.; Advanced Science Institute, RIKEN, Wako-shi, Saitama 351-0198; Nori, Franco

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.

Synergistic Enhancement of Microwave Absorption Using Hybridized Polyaniline@helical CNTs with Dual Chirality.

PubMed

Tian, Xin; Meng, Fanbin; Meng, Fanchen; Chen, Xiangnan; Guo, Yifan; Wang, Ying; Zhu, Wenjun; Zhou, Zuowan

2017-05-10

In this study, we designed a dual-chirality hierarchical structure to achieve a synergistically enhanced effect in microwave absorption via the hybridization of nanomaterials. Herein, polyaniline (PANi) nanorods with tunable chirality are grown on helical carbon nanotubes (HCNTs), a typical nanoscale chiral structure, through in situ polymerization. The experimental results show that the hierarchical hybrids (PANi@HCNTs) exhibit distinctly dual chirality and a significant enhancement in electromagnetic (EM) losses compared to those of either pure PANi or HCNTs. The maximum reflection loss of the as-prepared hybrids can reach -32.5 dB at 8.9 GHz. Further analysis demonstrates that combinations of chiral acid-doped PANi and coiled HCNTs with molecular and nanoscale chirality lead to synergistic effects resulting from the dual chirality. The so-called cross-polarization may result in additional interactions with induced EM waves in addition to multiscaled relaxations from functional groups and interfacial polarizations, which can benefit EM absorption.

Chiral recognition and selection during the self-assembly process of protein-mimic macroanions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yin, Panchao; Zhang, Zhi-Ming; Lv, Hongjin

The research on chiral recognition and chiral selection is not only fundamental in resolving the puzzle of homochirality, but also instructive in chiral separation and stereoselective catalysis. Here we report the chiral recognition and chiral selection during the self-assembly process of two enantiomeric wheel-shaped macroanions, [Fe28(μ3-O)8(Tart)16(HCOO)24]20- (Tart=D- or L-tartaric acid tetra-anion). The enantiomers are observed to remain self-sorted and self-assemble into their individual assemblies in their racemic mixture solution. The addition of chiral co-anions can selectively suppress the self-assembly process of the enantiomeric macroanions, which is further used to separate the two enantiomers from their mixtures on the basis ofmore » the size difference between the monomers and the assemblies. We believe that delicate long-range electrostatic interactions could be responsible for such high-level chiral recognition and selection.« less

Suppression of Magnetic Quantum Tunneling in a Chiral Single-Molecule Magnet by Ferromagnetic Interactions.

PubMed

Lippert, Kai-Alexander; Mukherjee, Chandan; Broschinski, Jan-Philipp; Lippert, Yvonne; Walleck, Stephan; Stammler, Anja; Bögge, Hartmut; Schnack, Jürgen; Glaser, Thorsten

2017-12-18

Single-molecule magnets (SMMs) retain a magnetization without applied magnetic field for a decent time due to an energy barrier U for spin-reversal. Despite the success to increase U, the difficult to control magnetic quantum tunneling often leads to a decreased effective barrier U eff and a fast relaxation. Here, we demonstrate the influence of the exchange coupling on the tunneling probability in two heptanuclear SMMs hosting the same spin-system with the same high spin ground state S t = 21/2. A chirality-induced symmetry reduction leads to a switch of the Mn III -Mn III exchange from antiferromagnetic in the achiral SMM [Mn III 6 Cr III ] 3+ to ferromagnetic in the new chiral SMM RR [Mn III 6 Cr III ] 3+ . Multispin Hamiltonian analysis by full-matrix diagonalization demonstrates that the ferromagnetic interactions in RR [Mn III 6 Cr III ] 3+ enforce a well-defined S t = 21/2 ground state with substantially less mixing of M S substates in contrast to [Mn III 6 Cr III ] 3+ and no tunneling pathways below the top of the energy barrier. This is experimentally verified as U eff is smaller than the calculated energy barrier U in [Mn III 6 Cr III ] 3+ due to tunneling pathways, whereas U eff equals U in RR [Mn III 6 Cr III ] 3+ demonstrating the absence of quantum tunneling.

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

PubMed

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

2017-04-18

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

Analyzing the Fierz rearrangement freedom for local chiral two-nucleon potentials

NASA Astrophysics Data System (ADS)

Huth, L.; Tews, I.; Lynn, J. E.; Schwenk, A.

2017-11-01

Chiral effective field theory is a framework to derive systematic nuclear interactions. It is based on the symmetries of quantum chromodynamics and includes long-range pion physics explicitly, while shorter-range physics is expanded in a general operator basis. The number of low-energy couplings at a particular order in the expansion can be reduced by exploiting the fact that nucleons are fermions and therefore obey the Pauli exclusion principle. The antisymmetry permits the selection of a subset of the allowed contact operators at a given order. When local regulators are used for these short-range interactions, however, this "Fierz rearrangement freedom" is violated. In this paper, we investigate the impact of this violation at leading order (LO) in the chiral expansion. We construct LO and next-to-leading order (NLO) potentials for all possible LO-operator pairs and study their reproduction of phase shifts, the 4He ground-state energy, and the neutron-matter energy at different densities. We demonstrate that the Fierz rearrangement freedom is partially restored at NLO where subleading contact interactions enter. We also discuss implications for local chiral three-nucleon interactions.

Chiral twist drives raft formation and organization in membranes composed of rod-like particles

PubMed Central

Lubensky, Tom C.

2017-01-01

Lipid rafts are hypothesized to facilitate protein interaction, tension regulation, and trafficking in biological membranes, but the mechanisms responsible for their formation and maintenance are not clear. Insights into many other condensed matter phenomena have come from colloidal systems, whose micron-scale particles mimic basic properties of atoms and molecules but permit dynamic visualization with single-particle resolution. Recently, experiments showed that bidisperse mixtures of filamentous viruses can self-assemble into colloidal monolayers with thermodynamically stable rafts exhibiting chiral structure and repulsive interactions. We quantitatively explain these observations by modeling the membrane particles as chiral liquid crystals. Chiral twist promotes the formation of finite-sized rafts and mediates a repulsion that distributes them evenly throughout the membrane. Although this system is composed of filamentous viruses whose aggregation is entropically driven by dextran depletants instead of phospholipids and cholesterol with prominent electrostatic interactions, colloidal and biological membranes share many of the same physical symmetries. Chiral twist can contribute to the behavior of both systems and may account for certain stereospecific effects observed in molecular membranes. PMID:27999184

Handedness Dependent Electromagnetically Induced Transparency in Hybrid Chiral Metamaterials

NASA Astrophysics Data System (ADS)

Kang, Lei; Hao Jiang, Zhi; Yue, Taiwei; Werner, Douglas H.

2015-07-01

We provide the first experimental demonstration of the handedness dependent electromagnetically induced transparency (EIT) in chiral metamaterials during the interaction with circularly polarized waves. The observed chiral-sensitive EIT phenomena arise from the coherent excitation of a non-radiative mode in the component split ring resonators (SRRs) produced by the corresponding Born-Kuhn type (radiative) resonators that are responsible for the pronounced chirality. The coherent coupling, which is dominated by the bonding and antibonding resonances of the Born-Kuhn type resonators, leads to an extremely steep dispersion for a circularly polarized wave of predefined handedness. Accordingly, retrieved effective medium parameters from simulated results further reveal a difference of 80 in the group indices for left- and right-handed circularly polarized waves at frequencies within the EIT window, which can potentially result in handedness-sensitive pulse delays. These chiral metamaterials which enable a handedness dependent EIT effect may provide more degrees of freedom for designing circular polarization based communication devices.

Assembly of mesoscale helices with near-unity enantiomeric excess and light-matter interactions for chiral semiconductors

PubMed Central

Feng, Wenchun; Kim, Ji-Young; Wang, Xinzhi; Calcaterra, Heather A.; Qu, Zhibei; Meshi, Louisa; Kotov, Nicholas A.

2017-01-01

Semiconductors with chiral geometries at the nanoscale and mesoscale provide a rich materials platform for polarization optics, photocatalysis, and biomimetics. Unlike metallic and organic optical materials, the relationship between the geometry of chiral semiconductors and their chiroptical properties remains, however, vague. Homochiral ensembles of semiconductor helices with defined geometries open the road to understanding complex relationships between geometrical parameters and chiroptical properties of semiconductor materials. We show that semiconductor helices can be prepared with an absolute yield of ca 0.1% and an enantiomeric excess (e.e.) of 98% or above from cysteine-stabilized cadmium telluride nanoparticles (CdTe NPs) dispersed in methanol. This high e.e. for a spontaneously occurring chemical process is attributed to chiral self-sorting based on the thermodynamic preference of NPs to assemble with those of the same handedness. The dispersions of homochiral self-assembled helices display broadband visible and near-infrared (Vis-NIR) polarization rotation with anisotropy (g) factors approaching 0.01. Calculated circular dichroism (CD) spectra accurately reproduced experimental CD spectra and gave experimentally validated spectral predictions for different geometrical parameters enabling de novo design of chiroptical semiconductor materials. Unlike metallic, ceramic, and polymeric helices that serve predominantly as scatterers, chiroptical properties of semiconductor helices have nearly equal contribution of light absorption and scattering, which is essential for device-oriented, field-driven light modulation. Deconstruction of a helix into a series of nanorods provides a simple model for the light-matter interaction and chiroptical activity of helices. This study creates a framework for further development of polarization-based optics toward biomedical applications, telecommunications, and hyperspectral imaging. PMID:28275728

Degenerate and chiral states in the extended Heisenberg model on the kagome lattice

NASA Astrophysics Data System (ADS)

Gómez Albarracín, F. A.; Pujol, P.

2018-03-01

We present a study of the low-temperature phases of the antiferromagnetic extended classical Heisenberg model on the kagome lattice, up to third-nearest neighbors. First, we focus on the degenerate lines in the boundaries of the well-known staggered chiral phases. These boundaries have either semiextensive or extensive degeneracy, and we discuss the partial selection of states by thermal fluctuations. Then, we study the model under an external magnetic field on these lines and in the staggered chiral phases. We pay particular attention to the highly frustrated point, where the three exchange couplings are equal. We show that this point can be mapped to a model with spin-liquid behavior and nonzero chirality. Finally, we explore the effect of Dzyaloshinskii-Moriya (DM) interactions in two ways: a homogeneous and a staggered DM interaction. In both cases, there is a rich low-temperature phase diagram, with different spontaneously broken symmetries and nontrivial chiral phases.

The engagement of optical angular momentum in nanoscale chirality

NASA Astrophysics Data System (ADS)

Andrews, David L.

2017-09-01

Wide-ranging developments in optical angular momentum have recently led to refocused attention on issues of material chirality. The connection between optical spin and circular polarization, linking to well-known and utilized probes of chirality such as circular dichroism, has prompted studies aiming to achieve enhanced means of differentiating enantiomers - molecules or particles of opposite handedness. A number of newly devised schemes for physically separating mirror-image components by optical methods have also been gaining traction, together with a developing appreciation of how the scale of physical dimensions ultimately determines any capacity to differentially select for material chirality. The scope of such enquiries has substantially widened on recognition that suitably structured, topologically charged beams of light - often known as `twisted light' or `optical vortices' can additionally convey orbital angular momentum. A case can be made that understanding the full scope and constraints upon chiroptical interactions in the nanoscale regime involves the resolution of CPT symmetry conditions governing the fundamental interactions between matter and photons. The principles provide a sound theoretical test-bed for new methodologies.

A loop-gap resonator for chirality-sensitive nuclear magneto-electric resonance (NMER)

NASA Astrophysics Data System (ADS)

Garbacz, Piotr; Fischer, Peer; Krämer, Steffen

2016-09-01

Direct detection of molecular chirality is practically impossible by methods of standard nuclear magnetic resonance (NMR) that is based on interactions involving magnetic-dipole and magnetic-field operators. However, theoretical studies provide a possible direct probe of chirality by exploiting an enantiomer selective additional coupling involving magnetic-dipole, magnetic-field, and electric field operators. This offers a way for direct experimental detection of chirality by nuclear magneto-electric resonance (NMER). This method uses both resonant magnetic and electric radiofrequency (RF) fields. The weakness of the chiral interaction though requires a large electric RF field and a small transverse RF magnetic field over the sample volume, which is a non-trivial constraint. In this study, we present a detailed study of the NMER concept and a possible experimental realization based on a loop-gap resonator. For this original device, the basic principle and numerical studies as well as fabrication and measurements of the frequency dependence of the scattering parameter are reported. By simulating the NMER spin dynamics for our device and taking the 19F NMER signal of enantiomer-pure 1,1,1-trifluoropropan-2-ol, we predict a chirality induced NMER signal that accounts for 1%-5% of the standard achiral NMR signal.

Description and Evaluation of Chiral Interactive Sites on Bonded Cyclodextrin Stationary Phases for Liquid Chromatography

NASA Astrophysics Data System (ADS)

Beesley, Thomas E.

Development of chiral separations has been essential to the drug discovery and development process. The solubility requirements for a number of methods and/or the mobile phase requirements for application of certain detection systems have opened up many opportunities for cyclodextrin-based CSPs for liquid chromatography. Even though a few chiral stationary phases cover a wide area of enantioselectivity, they do not meet the entire needs of the industry. Cyclodextrin phases offer some unique mechanisms and opportunities to resolve chiral separation problems especially in the aqueous reversed-phase and non-aqueous polar organic modes. This chapter addresses the need to understand the chiral stationary phase structure, the mechanisms at work, and the role mobile phase composition plays in driving those mechanisms to produce enantioselectivity. In addition, the development of certain derivatives has played an essential part in expanding that basic role for certain chiral separations. What these derivatives contribute in concert with the basic structure is a critical part of the understanding to the effective use of these phases. During this study it was determined that the role of steric hindrance has been vastly underestimated, both to the extent that it has occurred and to its effectiveness for obtaining enantioselectivity. References to the entire 20-year history of the cyclodextrin phase development and application literature up to this current date have been reviewed and incorporated.

Dissipative vibrational model for chiral recognition in olfaction

NASA Astrophysics Data System (ADS)

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

2015-09-01

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

Silver Films with Hierarchical Chirality.

PubMed

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

2017-07-17

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

Chiral fermions in asymptotically safe quantum gravity

NASA Astrophysics Data System (ADS)

Meibohm, J.; Pawlowski, J. M.

2016-05-01

We study the consistency of dynamical fermionic matter with the asymptotic safety scenario of quantum gravity using the functional renormalisation group. Since this scenario suggests strongly coupled quantum gravity in the UV, one expects gravity-induced fermion self-interactions at energies of the Planck scale. These could lead to chiral symmetry breaking at very high energies and thus to large fermion masses in the IR. The present analysis which is based on the previous works (Christiansen et al., Phys Rev D 92:121501, 2015; Meibohm et al., Phys Rev D 93:084035, 2016), concludes that gravity-induced chiral symmetry breaking at the Planck scale is avoided for a general class of NJL-type models. We find strong evidence that this feature is independent of the number of fermion fields. This finding suggests that the phase diagram for these models is topologically stable under the influence of gravitational interactions.

Chiral fermions in asymptotically safe quantum gravity.

PubMed

Meibohm, J; Pawlowski, J M

2016-01-01

We study the consistency of dynamical fermionic matter with the asymptotic safety scenario of quantum gravity using the functional renormalisation group. Since this scenario suggests strongly coupled quantum gravity in the UV, one expects gravity-induced fermion self-interactions at energies of the Planck scale. These could lead to chiral symmetry breaking at very high energies and thus to large fermion masses in the IR. The present analysis which is based on the previous works (Christiansen et al., Phys Rev D 92:121501, 2015; Meibohm et al., Phys Rev D 93:084035, 2016), concludes that gravity-induced chiral symmetry breaking at the Planck scale is avoided for a general class of NJL-type models. We find strong evidence that this feature is independent of the number of fermion fields. This finding suggests that the phase diagram for these models is topologically stable under the influence of gravitational interactions.

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

PubMed

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

2007-05-05

The understanding of the interaction of chiral species with DNA or RNA is very important for the development of new tools in biology and of new drugs. Several cases in which chirality is a crucial point in determining the DNA binding mode are reviewed and discussed, with the aim of illustrating how chirality can be considered as a tool for improving the understanding of mechanisms and the effectiveness of nucleic acid recognition. The review is divided into two parts: the former describes examples of chiral species interacting with DNA: intercalators, metal complexes, and groove binders; the latter part is dedicated to chirality in DNA analogs, with discussion of phosphate stereochemistry and chirality of ribose substitutes, in particular of peptide nucleic acids (PNAs) for which a number of works have been published recently dealing with the effect of chirality in DNA recognition. The discussion is intended to show how enantiomeric recognition originates at the molecular level, by exploiting the enormous progresses recently achieved in the field of structural characterization of complexes formed by nucleic acid with their ligands by crystallographic and spectroscopic methods. Examples of application of the DNA binding molecules described and the role of chirality in DNA recognition relevant for biotechnology or medicinal chemistry are reported. (c) 2007 Wiley-Liss, Inc.

CAPILLARY ELECTROPHORESIS FOR ENANTIOMER SEPARATION AND MEASUREMENT OF ENANTIOSELECTIVITY OF CHIRAL POLLUTANTS IN THE ENVIRONMENT

EPA Science Inventory

Chiral pollutants exist as 2 species, -- enantiomers - that have identical physical and chemical properties except when they interact with enzymes or other chiral molecules; then they usually react selectively. This enantioselectivity results in different rates of microbial trans...

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

PubMed

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

2018-02-27

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

Nucleon Polarisabilities and Effective Field Theories

NASA Astrophysics Data System (ADS)

Griesshammer, Harald W.

2017-09-01

Low-energy Compton scattering probes the nucleon's two-photon response to electric and magnetic fields at fixed photon frequency and multipolarity. It tests the symmetries and strengths of the interactions between constituents, and with photons. For convenience, this energy-dependent information is often compressed into the two scalar dipole polarisabilities αE 1 and βM 1 at zero photon energy. These are fundamental quantities, and important for the proton charge radius puzzle and the Lamb shift of muonic hydrogen. Combined with emerging lattice QCD computations, they provide stringent tests for our understanding of hadron structure. Extractions of the proton and neutron polarisabilities from all published elastic data below 300 MeV in Chiral Effective Field Theory with explicit Δ (1232) are now available. This talk emphasises χEFT as natural bridge between lattice QCD and ongoing or approved efforts at HI γS, MAMI and MAX-lab. Chiral lattice extrapolations from mπ > 200 MeV to the physical point compare well to lattice computations. Combining χEFT with high-intensity experiments with polarised targets and polarised beams will extract not only scalar polarisabilities, but in particular the four so-far poorly explored spin-polarisabilities. These parametrise the stiffness of the spin in external electro-magnetic fields (nucleonic bi-refringence/Faraday effect). New chiral predictions for proton, deuteron and 3He observables show intriguing sensitivities on spin and neutron polarisabilities. Data consistency and a model-independent quantification of residual theory uncertainties by Bayesian analysis are also discussed. Proton-neutron differences explore the interplay between chiral symmetry breaking and short-distance Physics. Finally, I address their impact on the neutron-proton mass difference, big-bang nucleosynthesis, and their relevance for anthropic arguments. Supported in part by DOE DE-SC0015393 and George Washington University.

Chiral zinc phenylalanine nanofibers with fluorescence.

PubMed

Chen, Erdan; Guo, Beidou; Zhang, Baohong; Gan, Li-Hua; Gong, Jian Ru

2011-09-01

Chiral Zn(II)/D-,L-phenylalanine (Phe) bio-coordination polymer nanofibers with fluorescence were prepared by fast coordination-assisted assembly. The synthetic strategy is based on the fact that the Zn2+ ions were linked to oxygen atoms from carboxylate groups of the D- or L-amino acid by coordination interactions to form the chiral polymers. The Zn(II)/D-,L-Phe nanofibers had homogeneous diameters in the range of 700-900 nm and ultra-long length in several hundred micrometers, and the surface of the fiber was extremely smooth. In addition, the enantiomers of Zn(II)/Phe nanofibers exhibited both optical activity and fluorescent property in the solid state, which has great potential for application in the field of biomimetic nanofabrication and micro-/nano-optoelectronics.

Chiral gravitational waves and baryon superfluid dark matter

NASA Astrophysics Data System (ADS)

Alexander, Stephon; McDonough, Evan; Spergel, David N.

2018-05-01

We develop a unified model of darkgenesis and baryogenesis involving strongly interacting dark quarks, utilizing the gravitational anomaly of chiral gauge theories. In these models, both the visible and dark baryon asymmetries are generated by the gravitational anomaly induced by the presence of chiral primordial gravitational waves. We provide a concrete model of an SU(2) gauge theory with two massless quarks. In this model, the dark quarks condense and form a dark baryon charge superfluid (DBS), in which the Higgs-mode acts as cold dark matter. We elucidate the essential features of this dark matter scenario and discuss its phenomenological prospects.

Periodic chiral structures

NASA Technical Reports Server (NTRS)

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

1989-01-01

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

Role of chirality in peptide-induced formation of cholesterol-rich domains

PubMed Central

2005-01-01

The chiral specificity of the interactions of peptides that induce the formation of cholesterol-rich domains has not been extensively investigated. Both the peptide and most lipids are chiral, so there is a possibility that interactions between peptide and lipid could require chiral recognition. On the other hand, in our models with small peptides, the extent of folding of the peptide to form a specific binding pocket is limited. We have determined that replacing cholesterol with its enantiomer, ent-cholesterol, alters the modulation of lipid organization by peptides. The phase-transition properties of SOPC (1-stearoyl-2-oleoylphosphatidylcholine):cholesterol [in a 6:4 ratio with 0.2 mol% PtdIns(4,5)P2] are not significantly altered when ent-cholesterol replaces cholesterol. However, in the presence of 10 mol% of a 19-amino-acid, N-terminally myristoylated fragment (myristoyl-GGKLSKKKKGYNVNDEKAK-amide) of the protein NAP-22 (neuronal axonal membrane protein), the lipid mixture containing cholesterol undergoes separation into cholesterol-rich and cholesterol-depleted domains. This does not occur when ent-cholesterol replaces cholesterol. In another example, when N-acetyl-Leu-Trp-Tyr-Ile-Lys-amide (N-acetyl-LWYIK-amide) is added to SOPC:cholesterol (7:3 ratio), there is a marked increase in the transition enthalpy of the phospholipid, indicating separation of a cholesterol-depleted domain of SOPC. This phenomenon completely disappears when ent-cholesterol replaces cholesterol. The all-D-isomer of N-acetyl-LWYIK-amide also induces the formation of cholesterol-rich domains with natural cholesterol, but does so to a lesser extent with ent-cholesterol. Thus specific peptide chirality is not required for interaction with cholesterol-containing membranes. However, a specific chirality of membrane lipids is required for peptide-induced formation of cholesterol-rich domains. PMID:15929726

Chirality in adsorption on solid surfaces.

PubMed

Zaera, Francisco

2017-12-07

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

Field dependence of nonreciprocal magnons in chiral MnSi

NASA Astrophysics Data System (ADS)

Weber, T.; Waizner, J.; Tucker, G. S.; Georgii, R.; Kugler, M.; Bauer, A.; Pfleiderer, C.; Garst, M.; Böni, P.

2018-06-01

Spin waves in chiral magnetic materials are strongly influenced by the Dzyaloshinskii-Moriya interaction, resulting in intriguing phenomena like nonreciprocal magnon propagation and magnetochiral dichroism. Here, we study the nonreciprocal magnon spectrum of the archetypical chiral magnet MnSi and its evolution as a function of magnetic field covering the field-polarized and conical helix phase. Using inelastic neutron scattering, the magnon energies and their spectral weights are determined quantitatively after deconvolution with the instrumental resolution. In the field-polarized phase the imaginary part of the dynamical susceptibility χ''(ɛ ,q ) is shown to be asymmetric with respect to wave vectors q longitudinal to the applied magnetic field H , which is a hallmark of chiral magnetism. In the helimagnetic phase, χ''(ɛ ,q ) becomes increasingly symmetric with decreasing H due to the formation of helimagnon bands and the activation of additional spin-flip and non-spin-flip scattering channels. The neutron spectra are in excellent quantitative agreement with the low-energy theory of cubic chiral magnets with a single fitting parameter being the damping rate of spin waves.

Chiral quantum supercrystals with total dissymmetry of optical response

NASA Astrophysics Data System (ADS)

Baimuratov, Anvar S.; Gun'Ko, Yurii K.; Baranov, Alexander V.; Fedorov, Anatoly V.; Rukhlenko, Ivan D.

2016-03-01

Since chiral nanoparticles are much smaller than the optical wavelength, their enantiomers show little difference in the interaction with circularly polarized light. This scale mismatch makes the enhancement of enantioselectivity in optical excitation of nanoobjects a fundamental challenge in modern nanophotonics. Here we demonstrate that a strong dissymmetry of optical response from achiral nanoobjects can be achieved through their arrangement into chiral superstructures with the length scale comparable to the optical wavelength. This concept is illustrated by the example of the simple helix supercrystal made of semiconductor quantum dots. We show that this supercrystal almost fully absorbs light with one circular polarization and does not absorb the other. The giant circular dichroism of the supercrystal comes from the formation of chiral bright excitons, which are the optically active collective excitations of the entire supercrystal. Owing to the recent advances in assembly and self-organization of nanocrystals in large superparticle structures, the proposed principle of enantioselectivity enhancement has great potential of benefiting various chiral and analytical methods, which are used in biophysics, chemistry, and pharmaceutical science.

Theory of Magnetic Edge States in Chiral Graphene Nanoribbons

NASA Astrophysics Data System (ADS)

Capaz, Rodrigo; Yazyev, Oleg; Louie, Steven

2011-03-01

Using a model Hamiltonian approach including electron Coulomb interactions, we systematically investigate the electronic structure and magnetic properties of chiral graphene nanoribbons. We show that the presence of magnetic edge states is an intrinsic feature of any smooth graphene nanoribbons with chiral edges, and discover a number of structure-property relations. Specifically, we describe how the edge-state energy gap, zone-boundary edge-state energy splitting, and magnetic moment per edge length depend on the nanoribbon width and chiral angle. The role of environmental screening effects is also studied. Our results address a recent experimental observation of signatures of magnetic ordering at smooth edges of chiral graphene nanoribbons and provide an avenue towards tuning their properties via the structural and environmental degrees of freedom. This work was supported by National Science Foundation Grant No. DMR10-1006184, the U.S. Department of Energy under Contract No. DE-AC02-05CH11231 and the ONR MURI program. RBC acknowledges financial support from Brazilian agencies CNPq, FAPERJ and INCT-Nanomateriais de Carbono.

Pattern production through a chiral chasing mechanism

NASA Astrophysics Data System (ADS)

Woolley, Thomas E.

2017-09-01

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

Chirality in microbial biofilms is mediated by close interactions between the cell surface and the substratum

PubMed Central

Jauffred, Liselotte; Munk Vejborg, Rebecca; Korolev, Kirill S; Brown, Stanley; Oddershede, Lene B

2017-01-01

From microbial biofilms to human migrations, spatial competition is central to the evolutionary history of many species. The boundary between expanding populations is the focal point of competition for space and resources and is of particular interest in ecology. For all Escherichia coli strains studied here, these boundaries move in a counterclockwise direction even when the competing strains have the same fitness. We find that chiral growth of bacterial colonies is strongly suppressed by the expression of extracellular features such as adhesive structures and pili. Experiments with other microbial species show that chiral growth is found in other bacteria and exclude cell wall biosynthesis and anisotropic shape as the primary causes of chirality. Instead, intimate contact with the substratum is necessary for chirality. Our results demonstrate that through a handful of surface molecules cells can fundamentally reorganize their migration patterns, which might affect intra- and interspecific competitions through colony morphology or other mechanisms. PMID:28362723

Chiral Magnetic Effect in Condensed Matters

NASA Astrophysics Data System (ADS)

Li, Qiang

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 chiral anomaly in systems possessing charged chiral fermions. In quark-gluon plasma containing nearly massless quarks, the chirality imbalance is sourced by the topological transitions. In condensed matter systems, the chiral quasiparticles emerge in the 3D Dirac and Weyl semimetals having a linear dispersion relation. Recently, the chiral magnetic effect was discovered in a 3D Dirac semimetal - zirconium pentatelluride, ZrTe5, in which a large negative magnetoresistance is observed when magnetic field is parallel with the current. It is now reported in more than a dozen Dirac and Weyl semimetals. Broadly speaking, the chiral magnetic effect can exist in a variety of condensed matters. In some cases, a material may be transformed into a Weyl semimetal by magnetic field, exhibiting the chiral magnetic effect. In other cases, the chiral magnetic current may be generated in magnetic Dirac semimetals without external magnetic field, or in asymmetric Weyl semimetals without electric field where only a magnetic field and the source of chiral quasipartiles would be necessary. In the limit of conserved quasiparticle chirality, charge transport by the chiral magnetic current is non-dissipative. The powerful notion of chirality, originally discovered in high-energy and nuclear physics, holds promise in new ways of transmitting and processing information and energy. At the same time, chiral materials have opened a fascinating possibility to study the quantum dynamics of relativistic field theory in condensed matter experiments.

Chiral optical response of planar and symmetric nanotrimers enabled by heteromaterial selection.

PubMed

Banzer, Peter; Woźniak, Paweł; Mick, Uwe; De Leon, Israel; Boyd, Robert W

2016-10-13

Chirality is an intriguing property of certain molecules, materials or artificial nanostructures, which allows them to interact with the spin angular momentum of the impinging light field. Due to their chiral geometry, they can distinguish between left- and right-hand circular polarization states or convert them into each other. Here we introduce an approach towards optical chirality, which is observed in individual two-dimensional and geometrically mirror-symmetric nanostructures. In this scheme, the chiral optical response is induced by the chosen heterogeneous material composition of a particle assembly and the corresponding resonance behaviour of the constituents it is built from, which breaks the symmetry of the system. As a proof of principle, we investigate such a structure composed of individual silicon and gold nanoparticles both experimentally, as well as numerically. Our proposed concept constitutes an approach for designing two-dimensional chiral media tailored at the nanoscale, allowing for high tunability of their optical response.

Chiral optical response of planar and symmetric nanotrimers enabled by heteromaterial selection

PubMed Central

Banzer, Peter; Woźniak, Paweł; Mick, Uwe; De Leon, Israel; Boyd, Robert W.

2016-01-01

Chirality is an intriguing property of certain molecules, materials or artificial nanostructures, which allows them to interact with the spin angular momentum of the impinging light field. Due to their chiral geometry, they can distinguish between left- and right-hand circular polarization states or convert them into each other. Here we introduce an approach towards optical chirality, which is observed in individual two-dimensional and geometrically mirror-symmetric nanostructures. In this scheme, the chiral optical response is induced by the chosen heterogeneous material composition of a particle assembly and the corresponding resonance behaviour of the constituents it is built from, which breaks the symmetry of the system. As a proof of principle, we investigate such a structure composed of individual silicon and gold nanoparticles both experimentally, as well as numerically. Our proposed concept constitutes an approach for designing two-dimensional chiral media tailored at the nanoscale, allowing for high tunability of their optical response. PMID:27734960

Photoremovable chiral auxiliary.

PubMed

Kammath, Viju Balachandran; Sebej, Peter; Slanina, Tomáš; Kříž, Zdeněk; Klán, Petr

2012-03-01

A new concept of a photoremovable chiral auxiliary (PCA), based on the chiral benzoin chromophore, is introduced. This moiety can control the asymmetric formation of a Diels-Alder adduct, and then be removed in a subsequent photochemical step in high chemical and quantum yields. Selective formation of the products at up to 96% ee was observed in the presence of a Lewis acid catalyst in the case of a 2-methoxybenzoinyl chiral auxiliary.

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.

Maltodextrins as chiral selectors in CE: molecular structure effect of basic chiral compounds on the enantioseparation.

PubMed

Tabani, Hadi; Fakhari, Ali Reza; Nojavan, Saeed

2014-10-01

Prediction of chiral separation for a compound using a chiral selector is an interesting and debatable work. For this purpose, in this study 23 chiral basic drugs with different chemical structures were selected as model solutes and the influence of their chemical structures on the enantioseparation in the presence of maltodextrin (MD) as chiral selector was investigated. For chiral separation, a 100-mM phosphate buffer solution (pH 3.0) containing 10% (w/v) MD with dextrose equivalent (DE) of 4-7 as chiral selector at the temperature of 25°C and voltage of 20 kV was used. Under this condition, baseline separation was achieved for nine chiral compounds and partial separation was obtained for another six chiral compounds while no enantioseparation was obtained for the remaining eight compounds. The results showed that the existence of at least two aromatic rings or cycloalkanes and an oxygen or nitrogen atom or -CN group directly bonded to the chiral center are necessary for baseline separation. With the obtained results in this study, chiral separation of a chiral compound can be estimated with MD-modified capillary electrophoresis before analysis. This prediction will minimize the number of preliminary experiments required to resolve enantiomers and will save time and cost. © 2014 Wiley Periodicals, Inc.

Meta-Chirality: Fundamentals, Construction and Applications

PubMed Central

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

2017-01-01

Chiral metamaterials represent a special type of artificial structures that cannot be superposed to their mirror images. Due to the lack of mirror symmetry, cross-coupling between electric and magnetic fields exist in chiral mediums and present unique electromagnetic characters of circular dichroism and optical activity, which provide a new opportunity to tune polarization and realize negative refractive index. Chiral metamaterials have attracted great attentions in recent years and have given rise to a series of applications in polarization manipulation, imaging, chemical and biological detection, and nonlinear optics. Here we review the fundamental theory of chiral media and analyze the construction principles of some typical chiral metamaterials. Then, the progress in extrinsic chiral metamaterials, absorbing chiral metamaterials, and reconfigurable chiral metamaterials are summarized. In the last section, future trends in chiral metamaterials and application in nonlinear optics are introduced. PMID:28513560

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

Dissymmetry effects on the laser spectroscopy of supersonically expanded rare gas/chiral arene heteroclusters.

PubMed

Filippi, Antonello; Giardini, Anna; Marcantoni, Enrico; Paladini, Alessandra; Piccirillo, Susanna; Renzi, Gabriele; Rondino, Flaminia; Roselli, Graziella; Satta, Mauro; Speranza, Maurizio

2007-04-14

The R2PI-TOF spectra of supersonically expanded rare gas/chiral arene heteroclusters have been rationalized in terms of the distortion of the pi-electron density reflecting the different dipole and quadrupole momenta induced in the rare gas atoms by interaction with the opposite pi-faces of the chiral arene itself.

Chirality-controlled crystallization via screw dislocations.

PubMed

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

2018-04-11

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

Chirality-selected phase behaviour in ionic polypeptide complexes

DOE PAGES

Perry, Sarah L.; Leon, Lorraine; Hoffmann, Kyle Q.; ...

2015-01-14

In this study, polyelectrolyte complexes present new opportunities for self-assembled soft matter. Factors determining whether the phase of the complex is solid or liquid remain unclear. Ionic polypeptides enable examination of the effects of stereochemistry on complex formation. Here we demonstrate that chirality determines the state of polyelectrolyte complexes, formed from mixing dilute solutions of oppositely charged polypeptides, via a combination of electrostatic and hydrogen-bonding interactions. Fluid complexes occur when at least one of the polypeptides in the mixture is racemic, which disrupts backbone hydrogen-bonding networks. Pairs of purely chiral polypeptides, of any sense, form compact, fibrillar solids with amore » β-sheet structure. Analogous behaviour occurs in micelles formed from polypeptide block copolymers with polyethylene oxide, where assembly into aggregates with either solid or fluid cores, and eventually into ordered phases at high concentrations, is possible. Chirality is an exploitable tool for manipulating material properties in polyelectrolyte complexation.« less

Chiral Recognition with Macrocyclic Glycopeptides: Mechanisms and Applications

NASA Astrophysics Data System (ADS)

Berthod, Alain; Qiu, Hai Xiao; Staroverov, Sergey M.; Kuznestov, Mikhail A.; Armstrong, Daniel W.

The macrocyclic glycopeptide chiral selectors are natural molecules produced by bacterial fermentation. Purified and bonded to silica particles, they make very useful chiral stationary phases (CSP) with a broad spectrum of applicability in enantiomeric separation. The macrocyclic glycopeptide CSPs are multimodal, the same column being able to work in normal phase mode with apolar mobile phase, in reversed-phase mode, or in polar ionic mode with 100% alcoholic mobile phase of adjusted pH. The role of the carbohydrate units is described as well as the critical charge-charge docking interaction responsible for the amino acid enantiomer recognition. The complimentary phenomenon is also exposed.

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

PubMed

Belinsky, Moisey I

2016-05-02

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

Advanced Command Destruct System (ACDS) Enhanced Flight Termination System (EFTS)

NASA Technical Reports Server (NTRS)

Tow, David

2009-01-01

NASA Dryden started working towards a single vehicle enhanced flight termination system (EFTS) in January 2008. NASA and AFFTC combined their efforts to work towards final operating capability for multiple vehicle and multiple missions simultaneously, to be completed by the end of 2011. Initially, the system was developed to support one vehicle and one frequency per mission for unmanned aerial vehicles (UAVs) at NASA Dryden. By May 2008 95% of design and hardware builds were completed, however, NASA Dryden's change of software safety scope and requirements caused delays after May 2008. This presentation reviews the initial and final operating capabilities for the Advanced Command Destruct System (ACDS), including command controller and configuration software development. A requirements summary is also provided.

Chirality and protein biosynthesis.

PubMed

Banik, Sindrila Dutta; Nandi, Nilashis

2013-01-01

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

Low-Energy Collisions of Protonated Enantiopure Amino Acids with Chiral Target Gases

NASA Astrophysics Data System (ADS)

Kulyk, K.; Rebrov, O.; Ryding, M.; Thomas, R. D.; Uggerud, E.; Larsson, M.

2017-12-01

Here we report on the gas-phase interactions between protonated enantiopure amino acids ( l- and d-enantiomers of Met, Phe, and Trp) and chiral target gases [( R)- and ( S)-2-butanol, and ( S)-1-phenylethanol] in 0.1-10.0 eV low-energy collisions. Two major processes are seen to occur over this collision energy regime, collision-induced dissociation and ion-molecule complex formation. Both processes were found to be independent of the stereo-chemical composition of the interacting ions and targets. These data shed light on the currently debated mechanisms of gas-phase chiral selectivity by demonstrating the inapplicability of the three-point model to these interactions, at least under single collision conditions. [Figure not available: see fulltext.

Recent advances in chirally pure proton pump inhibitors.

PubMed

Pai, Vikas; Pai, Nitin

2007-08-01

Chirality is a ubiquitous natural phenomenon resulting because of a differential spatial orientation of molecules around its chiral centre. This leads to the existence of two or more spatially dissimilar forms, known as stereoisomers or enantiomers, which are non-superimposable images of each other and may significantly differ from each other with respect to pharmacokinetic and pharmacodynamic properties and molecular interaction. Thus one isomer may offer significant pharmacokinetic and therapeutic advantages as compared to the other isomer or the racemic mixture (mixture containing both enantiomers). Proton pump inhibitors are a class of drugs which have been very effective in the management of acid-related disorders. The proton pumps currently available in the market including omeprazole, pantoprazole, rabeprazole and lansoprazole are racemic mixtures of the S and R isomers. Chirally pure forms of proton pump inhibitors show a superior metabolic and pharmacokinetic profile as compared to their racemates. The therapeutic efficacy is also superior to the parent racemate. This has been clearly demonstrated with the development of esomeprazole- the S-isomer of omeprazole. S-pantoprazole and dexrabeprazole also offer therapeutic advantages as compared to racemic pantoprazole and racemic rabeprazole respectively. This article reviews the chiral developments in the proton pump inhibitors and their clinical applications.

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

PubMed

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

2016-11-21

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

Timoshenko beam model for chiral materials

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Timoshenko beam model for chiral materials

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

Lattice spin models for non-Abelian chiral spin liquids

DOE PAGES

Lecheminant, P.; Tsvelik, A. M.

2017-04-26

Here, we suggest a class of two-dimensional lattice spin Hamiltonians describing non-Abelian SU(2) chiral spin liquids—spin analogs of fractional non-Abelian quantum Hall states—with gapped bulk and gapless chiral edge excitations described by the SU(2) n Wess-Zumino-Novikov-Witten conformal field theory. The models are constructed from an array of generalized spin-n/2 ladders with multi-spin-exchange interactions which are coupled by isolated spins. Such models allow a controllable analytic treatment starting from the one-dimensional limit and are characterized by a bulk gap and non-Abelian SU(2) n gapless edge excitations.

Transport and collective radiance in a basic quantum chiral optical model

NASA Astrophysics Data System (ADS)

Kornovan, D. F.; Petrov, M. I.; Iorsh, I. V.

2017-09-01

In our work, we theoretically study the dynamics of a single excitation in a one-dimensional array of two-level systems, which are chirally coupled through a single mode waveguide. The chirality is achieved owing to a strong optical spin-locking effect, which in an ideal case gives perfect unidirectional excitation transport. We obtain a simple analytical solution for a single excitation dynamics in the Markovian limit, which directly shows the tolerance of the system with respect to the fluctuations of emitters position. We also show that the Dicke state, which is well known to be superradiant, has twice lower emission rate in the case of unidirectional quantum interaction. Our model is supported and verified with the numerical computations of quantum emitters coupled via surface plasmon modes in a metallic nanowire. The obtained results are based on a very general model and can be applied to any chirally coupled system that gives a new outlook on quantum transport in chiral nanophotonics.

Three-dimensional plasmonic chiral tetramers assembled by DNA origami.

PubMed

Shen, Xibo; Asenjo-Garcia, Ana; Liu, Qing; Jiang, Qiao; García de Abajo, F Javier; Liu, Na; Ding, Baoquan

2013-05-08

Molecular chemistry offers a unique toolkit to draw inspiration for the design of artificial metamolecules. For a long time, optical circular dichroism has been exclusively the terrain of natural chiral molecules, which exhibit optical activity mainly in the UV spectral range, thus greatly hindering their significance for a broad range of applications. Here we demonstrate that circular dichroism can be generated with artificial plasmonic chiral nanostructures composed of the minimum number of spherical gold nanoparticles required for three-dimensional (3D) chirality. We utilize a rigid addressable DNA origami template to precisely organize four nominally identical gold nanoparticles into a three-dimensional asymmetric tetramer. Because of the chiral structural symmetry and the strong plasmonic resonant coupling between the gold nanoparticles, the 3D plasmonic assemblies undergo different interactions with left and right circularly polarized light, leading to pronounced circular dichroism. Our experimental results agree well with theoretical predictions. The simplicity of our structure geometry and, most importantly, the concept of resorting on biology to produce artificial photonic functionalities open a new pathway to designing smart artificial plasmonic nanostructures for large-scale production of optically active metamaterials.

Chiral Anomalous Dispersion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sadofyev, Andrey; Sen, Srimoyee

The linearized Einstein equation describing graviton propagation through a chiral medium appears to be helicity dependent. We analyze features of the corresponding spectrum in a collision-less regime above a flat background. In the long wave-length limit, circularly polarized metric perturbations travel with a helicity dependent group velocity that can turn negative giving rise to a new type of an anomalous dispersion. We further show that this chiral anomalous dispersion is a general feature of polarized modes propagating through chiral plasmas extending our result to the electromagnetic sector.

Chiral Anomalous Dispersion

DOE PAGES

Sadofyev, Andrey; Sen, Srimoyee

2018-02-16

The linearized Einstein equation describing graviton propagation through a chiral medium appears to be helicity dependent. We analyze features of the corresponding spectrum in a collision-less regime above a flat background. In the long wave-length limit, circularly polarized metric perturbations travel with a helicity dependent group velocity that can turn negative giving rise to a new type of an anomalous dispersion. We further show that this chiral anomalous dispersion is a general feature of polarized modes propagating through chiral plasmas extending our result to the electromagnetic sector.

Second Harmonic Generation Optical Rotation Solely Attributable to Chirality in Plasmonic Metasurfaces.

PubMed

Collins, Joel T; Hooper, David C; Mark, Andrew G; Kuppe, Christian; Valev, Ventsislav Kolev

2018-05-31

Chiral plasmonic nanostructures, those lacking mirror symmetry, can be designed to manipulate the polarization of incident light resulting in chiroptical (chiral optical) effects such as circular dichroism (CD) and optical rotation (OR). Due to high symmetry sensitivity, corresponding effects in second harmonic generation (SHG-CD and SHG-OR) are typically much stronger in comparison. These nonlinear effects have long been used for chiral molecular analysis and characterization, however both linear and nonlinear optical rotation can occur even in achiral structures, if the structure is birefringent due to anisotropy. Crucially, chiroptical effects resulting from anisotropy typically exhibit a strong dependence on structural orientation. Here we report large second-harmonic generation optical rotation of ±45°, due to intrinsic chirality in a highly anisotropic helical metamaterial. The SHG intensity is found to strongly relate to the structural anisotropy, however the angle of SHG-OR is invariant under sample rotation. We show that by tuning the geometry of anisotropic nanostructures, the interaction between anisotropy, chirality, and experiment geometry can allow even greater control over the chiroptical properties of plasmonic metamaterials.

Mass-Selective Chiral Analysis

NASA Astrophysics Data System (ADS)

Boesl, Ulrich; Kartouzian, Aras

2016-06-01

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

d +i d chiral superconductivity in a triangular lattice from trigonal bipyramidal complexes

NASA Astrophysics Data System (ADS)

Lu, Chen; Zhang, Li-Da; Wu, Xianxin; Yang, Fan; Hu, Jiangping

2018-04-01

We model the newly predicted high-Tc superconducting candidates constructed by corner-shared trigonal bipyramidal complexes with an effective three-orbital tight-binding Hamiltonian and investigate the pairing symmetry of their superconducting states driven by electron-electron interactions. Our combined weak- and strong-coupling-based calculations consistently identify the chiral d +i d superconductivity as the leading pairing symmetry in a wide doping range with realistic interaction parameters. This pairing state has a nontrivial topological Chern number and can host gapless chiral edge modes, and the vortex cores under magnetic field can carry Majorana zero modes.

Neutron matter with Quantum Monte Carlo: chiral 3N forces and static response

DOE PAGES

Buraczynski, M.; Gandolfi, S.; Gezerlis, A.; ...

2016-03-14

Neutron matter is related to the physics of neutron stars and that of neutron-rich nuclei. Moreover, Quantum Monte Carlo (QMC) methods offer a unique way of solving the many-body problem non-perturbatively, providing feedback on features of nuclear interactions and addressing scenarios that are inaccessible to other approaches. Our contribution goes over two recent accomplishments in the theory of neutron matter: a) the fusing of QMC with chiral effective field theory interactions, focusing on local chiral 3N forces, and b) the first attempt to find an ab initio solution to the problem of static response.

The effective chiral Lagrangian from the theta term

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mereghetti, E., E-mail: emanuele@physics.arizona.ed; Hockings, W.H., E-mail: whockings@bmc.ed; Kolck, U. van, E-mail: vankolck@physics.arizona.ed

2010-11-15

We construct the effective chiral Lagrangian involving hadronic and electromagnetic interactions originating from the QCD {theta}-bar term. We impose vacuum alignment at both quark and hadronic levels, including field redefinitions to eliminate pion tadpoles. We show that leading time-reversal-violating (TV) hadronic interactions are related to isospin-violating interactions that can in principle be determined from charge-symmetry-breaking experiments. We discuss the complications that arise from TV electromagnetic interactions. Some implications of the expected sizes of various pion-nucleon TV interactions are presented, and the pion-nucleon form factor is used as an example.

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

PubMed

Wernisch, Stefanie; Pell, Reinhard; Lindner, Wolfgang

2012-07-01

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

Enantioselective Effects of Chiral Pesticides on their Primary Targets and Secondary Targets.

PubMed

Yang, Ye; Zhang, Jianyun; Yao, Yijun

2017-01-01

Enantioselectivity has been well recognized in the environmental fate and effects of chiral pesticides. Enantiospecific action of the optical enantiomers on the biological molecules establishes the mechanistic basis for the enantioselective toxicity of chiral pesticides to both target and non-target organisms. We undertook a structured search of bibliographic databases for research literature concerning the enantioselective effects of chiral pesticides, including insecticides, herbicides and fungicides, on biomolecules in various species by using some key words. The results of the relevant literatures were reviewed in the text and summarized in tables. Pesticides generally exert their activity on the target organisms via disrupting the primary target biomolecules. In non-target species, effects of pesticides on the secondary targets distinguished from the primary ones make great contribution to their toxicity. Recent investigations have provided convincing evidence of enantioselective toxicity of chiral pesticides to both target and non-target species which is recognized to result from their enantiospecific action on the primary or secondary targets in organisms. This review confirms that chiral pesticides have enantiospecific effects on both primary and secondary target biomolecules in organisms. Future studies regarding toxicological effects of chiral pesticides should focus on the relationship between the enantiomeric difference in the compound-biomolecules interaction and the enantioselectivity in their toxicity.

Structural and electronic properties of chiral single-wall copper nanotubes

NASA Astrophysics Data System (ADS)

Duan, YingNi; Zhang, JianMin; Xu, KeWei

2014-04-01

The structural, energetic and electronic properties of chiral ( n, m) (3⩽ n⩽6, n/2⩽ m⩽ n) single-wall copper nanotubes (CuNTs) have been investigated by using projector-augmented wave method based on density-functional theory. The (4, 3) CuNT is energetically stable and should be observed experimentally in both free-standing and tip-suspended conditions, whereas the (5, 5) and (6, 4) CuNTs should be observed in free-standing and tip-suspended conditions, respectively. The number of conductance channels in the CuNTs does not always correspond to the number of atomic strands comprising the nanotube. Charge density contours show that there is an enhanced interatomic interaction in CuNTs compared with Cu bulk. Current transporting states display different periods and chirality, the combined effects of which lead to weaker chiral currents on CuNTs.

ISO(4,1) symmetry in the EFT of inflation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Creminelli, Paolo; Emami, Razieh; Simonović, Marko

In DBI inflation the cubic action is a particular linear combination of the two, otherwise independent, cubic operators π-dot {sup 3} and π-dot (∂{sub i}π){sup 2}. We show that in the Effective Field Theory (EFT) of inflation this is a consequence of an approximate 5D Poincar and apos;e symmetry, ISO(4,1), non-linearly realized by the Goldstone π. This symmetry uniquely fixes, at lowest order in derivatives, all correlation functions in terms of the speed of sound c{sub s}. In the limit c{sub s} → 1, the ISO(4,1) symmetry reduces to the Galilean symmetry acting on π. On the other hand, wemore » point out that the non-linear realization of SO(4,2), the isometry group of 5D AdS space, does not fix the cubic action in terms of c{sub s}.« less

The docking of chiral analytes on proline-based chiral stationary phases: A molecular dynamics study of selectivity.

PubMed

Ashtari, M; Cann, N M

2015-08-28

Molecular dynamics simulations are employed to examine the selectivity of four proline-based chiral stationary phases in two solvent environments, a relatively apolar n-hexane/2-propanol solvent and a polar water/methanol solvent. The four chiral surfaces are based on a BOC-terminated diproline, a TMA-terminated diproline, a TMA-terminated triproline and a TMA-terminated hexaproline. This range of chiral selectors allows an analysis of the impact of oligomer length and terminal group on selectivity while the two solvent environments indicate the impact of solvent hydrogen bonding and polarity. The selector-analyte interactions are examined for six closely related analytes that each have an aromatic moiety, a hydrogen, and an alcohol group directly bonded to the stereocenter. The analytes differ in the nature of the aromatic group (phenyl or anthracyl), in the attachment point (to the central ring or a side ring in the anthracyl), and in the fourth group bonded to the carbon (CH3, CF3, or C2H5). For each of the 48 solvent+selector+analyte systems, selectivity factors are calculated and, when possible, compared to experiment. The docking mode for these proline-based selectors is analyzed. Copyright © 2015 Elsevier B.V. All rights reserved.

Cell Chirality Drives Left-Right Asymmetric Morphogenesis.

PubMed

Inaki, Mikiko; Sasamura, Takeshi; Matsuno, Kenji

2018-01-01

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

Pure chiral optical fibres.

PubMed

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

2011-01-17

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

Magnetic vortex chirality determination via local hysteresis loops measurements with magnetic force microscopy

PubMed Central

Coïsson, Marco; Barrera, Gabriele; Celegato, Federica; Manzin, Alessandra; Vinai, Franco; Tiberto, Paola

2016-01-01

Magnetic vortex chirality in patterned square dots has been investigated by means of a field-dependent magnetic force microscopy technique that allows to measure local hysteresis loops. The chirality affects the two loop branches independently, giving rise to curves that have different shapes and symmetries as a function of the details of the magnetisation reversal process in the square dot, that is studied both experimentally and through micromagnetic simulations. The tip-sample interaction is taken into account numerically, and exploited experimentally, to influence the side of the square where nucleation of the vortex preferably occurs, therefore providing a way to both measure and drive chirality with the present technique. PMID:27426442

Magnetic vortex chirality determination via local hysteresis loops measurements with magnetic force microscopy.

PubMed

Coïsson, Marco; Barrera, Gabriele; Celegato, Federica; Manzin, Alessandra; Vinai, Franco; Tiberto, Paola

2016-07-18

Magnetic vortex chirality in patterned square dots has been investigated by means of a field-dependent magnetic force microscopy technique that allows to measure local hysteresis loops. The chirality affects the two loop branches independently, giving rise to curves that have different shapes and symmetries as a function of the details of the magnetisation reversal process in the square dot, that is studied both experimentally and through micromagnetic simulations. The tip-sample interaction is taken into account numerically, and exploited experimentally, to influence the side of the square where nucleation of the vortex preferably occurs, therefore providing a way to both measure and drive chirality with the present technique.

Magnetic vortex chirality determination via local hysteresis loops measurements with magnetic force microscopy

NASA Astrophysics Data System (ADS)

Coïsson, Marco; Barrera, Gabriele; Celegato, Federica; Manzin, Alessandra; Vinai, Franco; Tiberto, Paola

2016-07-01

Magnetic vortex chirality in patterned square dots has been investigated by means of a field-dependent magnetic force microscopy technique that allows to measure local hysteresis loops. The chirality affects the two loop branches independently, giving rise to curves that have different shapes and symmetries as a function of the details of the magnetisation reversal process in the square dot, that is studied both experimentally and through micromagnetic simulations. The tip-sample interaction is taken into account numerically, and exploited experimentally, to influence the side of the square where nucleation of the vortex preferably occurs, therefore providing a way to both measure and drive chirality with the present technique.

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.

Colloidal chirality in wormlike micellar systems exclusively originated from achiral species: Role of secondary assembly and stimulus responsivity.

PubMed

Zhao, Wenrong; Hao, Jingcheng

2016-09-15

Colloidal chirality in wormlike micellar systems exclusively originated from achiral species and discussion of the role of secondary assembly of fiber-like aggregates in chirality generation were presented in this paper. Herein, formation of colloidal wormlike micelles for the first time incorporated chirality and redox-responsiveness into one design via noncovalent interaction. A dual-stimuli-responsive gel of wormlike micelles which were designed by employing a dual-responsive cationic surfactant (FTMA) and a strong gelator (AzoNa4) and regulated by redox reaction and host-guest inclusion is presented. Both the redox and host-guest interaction play an important role in regulating the viscosity and supramolecular chirality of gels of the wormlike micelles. The supramolecular chirality and viscosity of the wormlike micelle gels were switched reversibly by exerting chemical redox onto the ferrocenyl groups. For the amphiphile FTMA containing redox-active ferrocenyl group, reversible control of the oxidation state of ferrocenyl groups leads to the charge and hydrophobicity changes of FTMA, therefore change its self-assembly behavior. Of equal interest, β-CD successfully detached the wormlike micelles via the recognition-inclusion behavior with FTMA and invalidate the H-bond and hydrophobic interaction between FTMA and AzoH4. This designed system provides a new strategy to tune the supramolecular chirality of colloidal aggregates and explore the specific packing mode detail within the micelles or the secondary assembly of the inter-micelles. We anticipate this dual-responsive H-bond-directed chiral gel switch could propose a new strategy when researchers designing new, multi-responsive functional gel materials. Copyright © 2016 Elsevier Inc. All rights reserved.

3D chiral nanoplasmonics: fabrication, chiroptic engineering, mechanism, and application in enantioselection (Presentation Recording)

NASA Astrophysics Data System (ADS)

Huang, Zhifeng

2015-09-01

Chirality does naturally exist, and the building blocks of life (e.g. DNA, proteins, peptides and sugars) are usually chiral. Chirality inherently imposes chemical/biological selectivity on functional molecules; hence the discrimination in molecular chirality from an enantiomer to the other mirror image (i.e. enantioselection) has fundamental and application significance. Enantiomers interact with left and right handed circularly polarized light in a different manner with respect to optical extinction; hence, electronic circular dichroism (ECD) has been widely used for enantioselection. However, enantiomers usually have remarkably low ECD intensity, mainly owing to the small electric transition dipole moment induced by molecular sizes compared to the ECD-active wavelength in the UV-visible-near IR region. To enhance ECD magnitude, recently it has being developed 3D chiral nanoplasmonic structures having a helical path, and the dimensions are comparable to the ECD wavelength. However, it is still ambiguous the origin of 3D chiroplasmonics, and there is a lack of studying the interaction of 3D chiroplasmoncs with enantiomers for the application of enantioselection. Herein, we will present a one-step fabrication of 3D silver nanospirals (AgNSs) via low-substrate-temperature glancing angle deposition. AgNSs can be deposited on a wide range of substrates (including transparent and flexible substrates), in an area on the order of cm2. A set of spiral dimensions (such as spiral pitches, number of turns and handedness) have been easily engineered to tune the chiroptic properties, leading to studying the chiroplasmonic principles together with finite element simulation and the LC model. At the end, it will be demonstrated that 3D chiroplasmonics can differentiate molecular chirality of enantiomers with dramatic enhancement in the anisotropy g factor. This study opens a door to sensitively discriminate enantiomer chirality.

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

Coriolis effect and spin Hall effect of light in an inhomogeneous chiral medium.

PubMed

Zhang, Yongliang; Shi, Lina; Xie, Changqing

2016-07-01

We theoretically investigate the spin Hall effect of spinning light in an inhomogeneous chiral medium. The Hamiltonian equations of the photon are analytically obtained within eikonal approximation in the noninertial orthogonal frame. Besides the usual spin curvature coupling, the chiral parameter enters the Hamiltonian as a spin-torsion-like interaction. We reveal that both terms have parallel geometric origins as the Coriolis terms of Maxwell's equations in nontrivial frames.

Chiral magnetic effect of light

NASA Astrophysics Data System (ADS)

Hayata, Tomoya

2018-05-01

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

Transfer and Dynamic Inversion of Coassembled Supramolecular Chirality through 2D-Sheet to Rolled-Up Tubular Structure.

PubMed

Choi, Heekyoung; Cho, Kang Jin; Seo, Hyowon; Ahn, Junho; Liu, Jinying; Lee, Shim Sung; Kim, Hyungjun; Feng, Chuanliang; Jung, Jong Hwa

2017-12-13

Transfer and inversion of supramolecular chirality from chiral calix[4]arene analogs (3D and 3L) with an alanine moiety to an achiral bipyridine derivative (1) with glycine moieties in a coassembled hydrogel are demonstrated. Molecular chirality of 3D and 3L could transfer supramolecular chirality to an achiral bipyridine derivative 1. Moreover, addition of 0.6 equiv of 3D or 3L to 1 induced supramolecular chirality inversion of 1. More interestingly, the 2D-sheet structure of the coassembled hydrogels formed with 0.2 equiv of 3D or 3L changed to a rolled-up tubular structure in the presence of 0.6 equiv of 3D or 3L. The chirality inversion and morphology change are mainly mediated by intermolecular hydrogen-bonding interactions between the achiral and chiral molecules, which might be induced by reorientations of the assembled molecules, confirmed by density functional theory calculations.

Micro-flock patterns and macro-clusters in chiral active Brownian disks

NASA Astrophysics Data System (ADS)

Levis, Demian; Liebchen, Benno

2018-02-01

Chiral active particles (or self-propelled circle swimmers) feature a rich collective behavior, comprising rotating macro-clusters and micro-flock patterns which consist of phase-synchronized rotating clusters with a characteristic self-limited size. These patterns emerge from the competition of alignment interactions and rotations suggesting that they might occur generically in many chiral active matter systems. However, although excluded volume interactions occur naturally among typical circle swimmers, it is not yet clear if macro-clusters and micro-flock patterns survive their presence. The present work shows that both types of pattern do survive but feature strongly enhance fluctuations regarding the size and shape of the individual clusters. Despite these fluctuations, we find that the average micro-flock size still follows the same characteristic scaling law as in the absence of excluded volume interactions, i.e. micro-flock sizes scale linearly with the single-swimmer radius.

The phi-meson and Chiral-mass-meson production in heavy-ion collisions as potential probes of quark-gluon-plasma and Chiral symmetry transitions

NASA Technical Reports Server (NTRS)

Takahashi, Y.; Eby, P. B.

1985-01-01

Possibilities of observing abundances of phi mesons and narrow hadronic pairs, as results of QGP and Chiral transitions, are considered for nucleus-nucleus interactions. Kinematical requirements in forming close pairs are satisfied in K+K decays of S(975) and delta (980) mesons with small phi, and phi (91020) mesons with large PT, and in pi-pi decays of familiar resonance mesons only in a partially restored chiral symmetry. Gluon-gluon dominance in QGP can enhance phi meson production. High hadronization rates of primordial resonance mesons which form narrow hadronic pairs are not implausible. Past cosmic ray evidences of anomalous phi production and narrow pair abundances are considered.

Cell Chirality Drives Left-Right Asymmetric Morphogenesis

PubMed Central

Inaki, Mikiko; Sasamura, Takeshi; Matsuno, Kenji

2018-01-01

Most macromolecules found in cells are chiral, meaning that they cannot be superimposed onto their mirror image. However, cells themselves can also be chiral, a subject that has received little attention until very recently. In our studies on the mechanisms of left-right (LR) asymmetric development in Drosophila, we discovered that cells can have an intrinsic chirality to their structure, and that this “cell chirality” is generally responsible for the LR asymmetric development of certain organs in this species. The actin cytoskeleton plays important roles in the formation of cell chirality. In addition, Myosin31DF (Myo31DF), which encodes Drosophila Myosin ID, was identified as a molecular switch for cell chirality. In other invertebrate species, including snails and Caenorhabditis elegans, chirality of the blastomeres, another type of cell chirality, determines the LR asymmetry of structures in the body. Thus, chirality at the cellular level may broadly contribute to LR asymmetric development in various invertebrate species. Recently, cell chirality was also reported for various vertebrate cultured cells, and studies suggested that cell chirality is evolutionarily conserved, including the essential role of the actin cytoskeleton. Although the biological roles of cell chirality in vertebrates remain unknown, it may control LR asymmetric development or other morphogenetic events. The investigation of cell chirality has just begun, and this new field should provide valuable new insights in biology and medicine. PMID:29666795

Chiral electroweak currents in nuclei

DOE PAGES

Riska, D. O.; Schiavilla, R.

2017-01-10

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

Five chiral Cd(II) complexes with dual chiral components: Effect of positional isomerism, luminescence and SHG response

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng, Lin, E-mail: lcheng@seu.edu.cn; Jiangsu Province Hi-Tech Key Laboratory for Bio-medical Research, Southeast University, Nanjing 211189; Wang, Jun

2015-01-15

Five chiral Cd(II) complexes with dual chiral components have been synthesized by using a series of (1R,2R)–N{sup 1},N{sup 2}-bis(pyridinylmethyl)cyclohexane-1,2-diamine ligands with different N-positions of pyridyl rings and Cd(NO{sub 3}){sub 2}. The circular dichroism (CD) spectra and second-harmonic generation (SHG) efficiency measurements confirmed that they are of structural chirality in the bulk samples. The luminescent properties indicated that they may have potential applications as optical materials. The formation of discrete mononuclear and binuclear complexes, and one-dimensional chains may be attributed to positional isomerism of the ligands. - Graphical abstract: Five chiral Cd(II) complexes with dual chiral components have been synthesized bymore » using a series of chiral ligands with different N-positions of pyridyl rings. - Highlights: • Five chiral Cd(II) complexes with dual chiral components have been synthesized. • CD spectra and SHG efficiency of the bulk samples have been measured. • The complexes display luminescent properties.« less

Chiral Plasmonic Nanostructures on Achiral Nanopillars

DTIC Science & Technology

2013-10-10

spherical nanoparticles where the particle−particle plasmonic interactions create CD and chiral plasmonic excitations.11,20,34 Since CPNs are vertically...Information Additional electron microscope images, CD spectra with silica nanoparticles , and UV−vis absorbance data. This material is available free of charge...materials based on individual nanoparticles (NPs)7,8 or their assemblies9,10 have attracted much attention because of the tunability of their absorption bands

Nanoscale chirality in metal and semiconductor nanoparticles

PubMed Central

Thomas, K. George

2016-01-01

The field of chirality has recently seen a rejuvenation due to the observation of chirality in inorganic nanomaterials. The advancements in understanding the origin of nanoscale chirality and the potential applications of chiroptical nanomaterials in the areas of optics, catalysis and biosensing, among others, have opened up new avenues toward new concepts and design of novel materials. In this article, we review the concept of nanoscale chirality in metal nanoclusters and semiconductor quantum dots, then focus on recent experimental and theoretical advances in chiral metal nanoparticles and plasmonic chirality. Selected examples of potential applications and an outlook on the research on chiral nanomaterials are additionally provided. PMID:27752651

Nanoscale chirality in metal and semiconductor nanoparticles.

PubMed

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

2016-10-18

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

Enantiomeric separation of six chiral pesticides that contain chiral sulfur/phosphorus atoms by supercritical fluid chromatography.

PubMed

Zhang, Lijun; Miao, Yelong; Lin, Chunmian

2018-03-01

Six chiral pesticides containing chiral sulfur/phosphorus atoms were separated by supercritical fluid chromatography with supercritical CO 2 as the main mobile phase component. The effect of the chiral stationary phase, different type and concentration of modifiers, column temperature, and backpressure on the separation efficiency was investigated to obtain the appropriate separation condition. Five chiral pesticides (isofenphos-methyl, isocarbophos, flufiprole, fipronil, and ethiprole) were baseline separated under experimental conditions, while isofenphos only obtained partial separation. The Chiralpak AD-3 column showed a better chiral separation ability than others for chiral pesticides containing chiral sulfur/phosphorus atoms. When different modifiers at the same concentration were used, the retention factor of pesticides except flufiprole decreased in the order of isopropanol, ethanol, methanol; meanwhile, the retention factor of flufiprole increased in the order of isopropanol, ethanol, methanol. For a given modifier, the retention factor and resolution decreased on the whole with the increase of its concentration. The enantiomer separation of five chiral pesticides was an "enthalpy-driven" process, and the separation factor decreased as the temperature increased. The backpressure of the mobile phase had little effect on the separation factor and resolution. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The goldstone and goldstino of supersymmetric inflation

DOE PAGES

Kahn, Yonatan; Roberts, Daniel A.; Thaler, Jesse

2015-10-01

Here, we construct the minimal effective field theory (EFT) of supersymmetric inflation, whose field content is a real scalar, the goldstone for time-translation breaking, and a Weyl fermion, the goldstino for supersymmetry (SUSY) breaking. The inflating background can be viewed as a single SUSY-breaking sector, and the degrees of freedom can be efficiently parameterized using constrained superfields. Our EFT is comprised of a chiral superfield X NL containing the goldstino and satisfying X 2 NL = 0, and a real superfield B NL containing both the goldstino and the goldstone, satisfying X NL B NL = B 3 NL =more » 0. We match results from our EFT formalism to existing results for SUSY broken by a fluid background, showing that the goldstino propagates with subluminal velocities. The same effect can also be derived from the unitary gauge gravitino action after embedding our EFT in supergravity. If the gravitino mass is comparable to the Hubble scale during inflation, we identify a new parameter in the EFT related to a time-dependent phase of the gravitino mass parameter. We briefly comment on the leading contributions of goldstino loops to inflationary observables.« less

Chiral templating of self-assembling nanostructures by circularly polarized light

DOE PAGES

Yeom, Jihyeon; Yeom, Bongjun; Chan, Henry; ...

2014-11-17

Chemical reactions affected by spin angular momenta of circularly polarized photons are rare and display low enantiomeric excess. High optical and chemical activity of nanoparticles (NPs) should facilitate the transfer of spin angular momenta of photons to nanoscale materials but such processes are unknown. Here we demonstrate that circularly polarized light (CPL) strongly affects self-assembly of racemic CdTe NPs. Illumination of NP dispersions with right- and left-handed CPL induces the formation of right- and left-handed twisted nanoribbons, respectively. Enantiomeric excess of such reactions exceeds 30% which is ~10 times higher than other CPL-induced reactions. Illumination with linearly polarized light andmore » assembly in the dark led to straight nanoribbons. The mechanism of “templation” of NP assemblies by CPL is associated with selective photoactivation of chiral NPs and clusters followed by their photooxidation. Chiral anisotropy of interactions translates into chirality of the assembled ribbons. Lastly, the ability of NPs to retain polarization information, or the “imprint” of incident photons opens new pathways for the synthesis of chiral photonic materials and allows for better understanding of the origins of biomolecular homochirality.« less

Chiral Templating of Self-Assembling Nanostructures by Circularly Polarized Light

PubMed Central

Yeom, Jihyeon; Yeom, Bongjun; Chan, Henry; Smith, Kyle W.; Dominguez-Medina, Sergio; Bahng, Joong Hwan; Zhao, Gongpu; Chang, Wei-Shun; Chang, Sung Jin; Chuvilin, Andrey; Melnikau, Dzmitry; Rogach, Andrey L.; Zhang, Peijun; Link, Stephan; Král, Petr; Kotov, Nicholas A.

2015-01-01

Chemical reactions affected by spin angular momenta of circularly polarized photons are rare and display low enantiomeric excess. High optical and chemical activity of nanoparticles (NPs) should facilitate the transfer of spin angular momenta of photons to nanoscale materials but such processes are unknown. Here we demonstrate that circularly polarized light (CPL) strongly affects self-assembly of racemic CdTe NPs. Illumination of NP dispersions with right- and left-handed CPL induces the formation of right- and left-handed twisted nanoribbons, respectively. Enantiomeric excess of such reactions exceeds 30% which is ~10 times higher than other CPL-induced reactions. Illumination with linearly polarized light and assembly in the dark led to straight nanoribbons. The mechanism of “templation” of NP assemblies by CPL is associated with selective photoactivation of chiral NPs and clusters followed by their photooxidation. Chiral anisotropy of interactions translates into chirality of the assembled ribbons. The ability of NPs to retain polarization information, or the “imprint” of incident photons opens new pathways for the synthesis of chiral photonic materials and allows for better understanding of the origins of biomolecular homochirality. PMID:25401922

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

PubMed

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

2014-01-21

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

Chiral amplification and sensing of chirality with lyotropic chromonic liquid crystals

NASA Astrophysics Data System (ADS)

Srinivasarao, Mohan; Park, Jung Ok; Fu, Jinxin; Nayani, Karthik; Chang, Rui

Due to the anisotropic elastic properties of lyotropic chromonic liquid crystals (LCLCs), a spontaneously twisted chiral structure has been reported in the achiral LCLCs system under cylindrical confinement. It is found that the handedness of chirality could be biased with a minute amount of a chiral additive. The entire system becomes ``homochiral'' and takes on the handedness of the additive. When 1% by weight of L-glutamic acid was added to LCLCs in a cylinder, the LCLC sbecomes homochiral and possesses giant optical rotation. We explore the mechanism for this based on the ``sergeants-and-soldiers'' and the ``majority-rule'' principles known for organic molecular systems.

Macdonald index and chiral algebra

NASA Astrophysics Data System (ADS)

Song, Jaewon

2017-08-01

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

Macdonald index and chiral algebra

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Jaewon

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

Macdonald index and chiral algebra

DOE PAGES

Song, Jaewon

2017-08-10

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

Electromagnetic wave propagation through a dielectric-chiral interface and through a chiral slab

NASA Technical Reports Server (NTRS)

Bassiri, S.; Papas, C. H.; Engheta, N.

1988-01-01

The reflection from and transmission through a semiinfinite chiral medium are analyzed by obtaining the Fresnel equations in terms of parallel- and perpendicular-polarized modes, and a comparison is made with results reported previously. The chiral medium is described electromagnetically by the constitutive relations D = (epsilon)E+i(gamma)B and H = i(gamma)E+(1/mu)B. The constants epsilon, mu and gamma are real and have values that are fixed by the size, the shape, and the spatial distribution of the elements that collectively compose the medium. The conditions are obtained for the total internal reflection of the incident wave from the interface and for the existence of the Brewster angle. The effects of the chirality on the polarization and the intensity of the reflected wave from the chiral half-space are discussed and illustrated by using the Stokes parameters. The propagation of electromagnetic wave through an infinite slab of chiral medium is formulated for oblique incidence and solved analytically for the case of normal incidence.

Lattice field theory study of magnetic catalysis in graphene

DOE PAGES

DeTar, Carleton; Winterowd, Christopher; Zafeiropoulos, Savvas

2017-04-15

We discuss the simulation of the low-energy effective field theory (EFT) for graphene in the presence of an external magnetic field. Our fully nonperturbative calculation uses methods of lattice gauge theory to study the theory using a hybrid Monte Carlo approach. We investigate the phenomenon of magnetic catalysis in the context of graphene by studying the chiral condensate which is the order parameter characterizing the spontaneous breaking of chiral symmetry. In the EFT, the symmetry breaking pattern is given bymore » $$U(4) \\to U(2) \\times U(2)$$. We also comment on the difficulty, in this lattice formalism, of studying the time-reversal-odd condensate characterizing the ground state in the presence of a magnetic field. Lastly, we study the mass spectrum of the theory, in particular the Nambu-Goldstone (NG) mode as well as the Dirac quasiparticle, which is predicted to obtain a dynamical mass.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

DeTar, Carleton; Winterowd, Christopher; Zafeiropoulos, Savvas

We discuss the simulation of the low-energy effective field theory (EFT) for graphene in the presence of an external magnetic field. Our fully nonperturbative calculation uses methods of lattice gauge theory to study the theory using a hybrid Monte Carlo approach. We investigate the phenomenon of magnetic catalysis in the context of graphene by studying the chiral condensate which is the order parameter characterizing the spontaneous breaking of chiral symmetry. In the EFT, the symmetry breaking pattern is given bymore » $$U(4) \\to U(2) \\times U(2)$$. We also comment on the difficulty, in this lattice formalism, of studying the time-reversal-odd condensate characterizing the ground state in the presence of a magnetic field. Lastly, we study the mass spectrum of the theory, in particular the Nambu-Goldstone (NG) mode as well as the Dirac quasiparticle, which is predicted to obtain a dynamical mass.« less

Out-of-equilibrium chiral magnetic effect from chiral kinetic theory

NASA Astrophysics Data System (ADS)

Huang, Anping; Jiang, Yin; Shi, Shuzhe; Liao, Jinfeng; Zhuang, Pengfei

2018-02-01

Recently there has been significant interest in the macroscopic manifestation of chiral anomaly in many-body systems of chiral fermions. A notable example is the Chiral Magnetic Effect (CME). Enthusiastic efforts have been made to search for the CME in the quark-gluon plasma created in heavy ion collisions. A crucial challenge is that the extremely strong magnetic field in such collisions may last only for a brief moment and the CME current may have to occur at so early a stage that the quark-gluon matter is still far from thermal equilibrium. This thus requires modeling of the CME in an out-of-equilibrium setting. With the recently developed theoretical tool of chiral kinetic theory, we make a first phenomenological study of the CME-induced charge separation during the pre-thermal stage in heavy ion collisions. The effect is found to be very sensitive to the time dependence of the magnetic field and also influenced by the initial quark momentum spectrum as well as the relaxation time of the system evolution toward thermal equilibrium. Within the present approach, such pre-thermal charge separation is found to be modest.

Chiral magnetic microspheres purified by centrifugal field flow fractionation and microspheres magnetic chiral chromatography for benzoin racemate separation

PubMed Central

Tian, Ailin; Qi, Jing; Liu, Yating; Wang, Fengkang; Ito, Yoichiro; Wei, Yun

2013-01-01

Separation of enantiomers still remains a challenge due to their identical physical and chemical properties in a chiral environment, and the research on specific chiral selector along with separation techniques continues to be conducted to resolve individual enantiomers. In our laboratory the promising magnetic chiral microspheres Fe3O4@SiO2@cellulose-2, 3-bis (3, 5-dimethylphenylcarbamate) have been developed to facilitate the resolution using both its magnetic property and chiral recognition ability. In our present studies this magnetic chiral selector was first purified by centrifuge field flow fractionation, and then used to separate benzoin racemate by a chromatographic method. Uniform-sized and masking-impurity-removed magnetic chiral selector was first obtained by field flow fractionation with ethanol through a spiral column mounted on the type-J planetary centrifuge, and using the purified magnetic chiral selector, the final chromatographic separation of benzoin racemate was successfully performed by eluting with ethanol through a coiled tube (wound around the cylindrical magnet to retain the magnetic chiral selector as a stationary phase) submerged in dry ice. In addition, an external magnetic field facilitates the recycling of the magnetic chiral selector. PMID:23891368

Chiral magnetic microspheres purified by centrifugal field flow fractionation and microspheres magnetic chiral chromatography for benzoin racemate separation.

PubMed

Tian, Ailin; Qi, Jing; Liu, Yating; Wang, Fengkang; Ito, Yoichiro; Wei, Yun

2013-08-30

Separation of enantiomers still remains a challenge due to their identical physical and chemical properties in a chiral environment, and the research on specific chiral selector along with separation techniques continues to be conducted to resolve individual enantiomers. In our laboratory the promising magnetic chiral microspheres Fe3O4@SiO2@cellulose-2, 3-bis (3,5-dimethylphenylcarbamate) have been developed to facilitate the resolution using both its magnetic property and chiral recognition ability. In our present studies this magnetic chiral selector was first purified by centrifuge field flow fractionation, and then used to separate benzoin racemate by a chromatographic method. Uniform-sized and masking-impurity-removed magnetic chiral selector was first obtained by field flow fractionation with ethanol through a spiral column mounted on the type-J planetary centrifuge, and using the purified magnetic chiral selector, the final chromatographic separation of benzoin racemate was successfully performed by eluting with ethanol through a coiled tube (wound around the cylindrical magnet to retain the magnetic chiral selector as a stationary phase) submerged in dry ice. In addition, an external magnetic field facilitates the recycling of the magnetic chiral selector. Copyright © 2013 Elsevier B.V. All rights reserved.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Braguta, V. V., E-mail: braguta@mail.ru; Buividovich, P. V., E-mail: buividovich@itep.ru; Kalaydzhyan, T., E-mail: tigran.kalaydzhyan@desy.de

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 ofmore » the chirality and electromagnetic current, which grow with the magnetic field strength. These fluctuations can be a manifestation of the Chiral Magnetic Effect.« less

Nematic and chiral superconductivity induced by odd-parity fluctuations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Fengcheng; Martin, Ivar

Recent experiments indicate that superconductivity in Bi 2Se 3 intercalated with Cu, Nb, or Sr is nematic with rotational symmetry breaking. Motivated by this observation, we present a model study of nematic and chiral superconductivity induced by odd-parity fluctuations. Additionally, we show that odd-parity fluctuations in the two-component E u representation of D 3d crystal point group can generate attractive interaction in both the even-parity s-wave and odd-parity E-u pairing channels, but repulsive interaction in other odd-parity pairing channels. Coulomb repulsion can suppress s-wave pairing relative to E u pairing, and thus the latter can have a higher critical temperature.more » E u pairing has two distinct phases: a nematic phase and a chiral phase, both of which can be realized in our model. Finally, when s-wave and E u pairings have similar instability temperature, we find an intermediate phase in which both types of pairing coexist.« less

Nematic and chiral superconductivity induced by odd-parity fluctuations

DOE PAGES

Wu, Fengcheng; Martin, Ivar

2017-10-09

Recent experiments indicate that superconductivity in Bi 2Se 3 intercalated with Cu, Nb, or Sr is nematic with rotational symmetry breaking. Motivated by this observation, we present a model study of nematic and chiral superconductivity induced by odd-parity fluctuations. Additionally, we show that odd-parity fluctuations in the two-component E u representation of D 3d crystal point group can generate attractive interaction in both the even-parity s-wave and odd-parity E-u pairing channels, but repulsive interaction in other odd-parity pairing channels. Coulomb repulsion can suppress s-wave pairing relative to E u pairing, and thus the latter can have a higher critical temperature.more » E u pairing has two distinct phases: a nematic phase and a chiral phase, both of which can be realized in our model. Finally, when s-wave and E u pairings have similar instability temperature, we find an intermediate phase in which both types of pairing coexist.« less

Effect of fenoterol stereochemistry on the β2 adrenergic receptor system: ligand-directed chiral recognition.

PubMed

Jozwiak, Krzysztof; Plazinska, Anita; Toll, Lawrence; Jimenez, Lucita; Woo, Anthony Yiu-Ho; Xiao, Rui-Ping; Wainer, Irving W

2011-01-01

The β(2) adrenergic receptor (β(2)-AR) is a model system for studying the ligand recognition process in G protein-coupled receptors. Fenoterol (FEN) is a β(2)-AR selective agonist that has two centers of chirality and exists as four stereoisomers. Radioligand binding studies determined that stereochemistry greatly influences the binding affinity. Subsequent Van't Hoff analysis shows very different thermodynamics of binding depending on the stereoconfiguration of the molecule. The binding of (S,x')-isomers is almost entirely enthalpy controlled whereas binding of (R,x')-isomers is purely entropy driven. Stereochemistry of FEN molecule also affects the coupling of the receptor to different G proteins. In a rat cardiomyocyte contractility model, (R,R')-FEN was shown to selectively activate G(s) protein signaling while the (S,R')-isomer activated both G(i) and G(s) protein. The overall data demonstrate that the chirality at the two chiral centers of the FEN molecule influences the magnitude of binding affinity, thermodynamics of local interactions within the binding site, and the global mechanism of β(2)-AR activation. Differences in thermodynamic parameters and nonuniform G-protein coupling suggest a mechanism of chiral recognition in which observed enantioselectivities arise from the interaction of the (R,x')-FEN stereoisomers with a different receptor conformation than the one with which the (S,x')-isomer interacts. Copyright © 2011 Wiley-Liss, Inc.

Chiral symmetry and π - π scattering in the Covariant Spectator Theory

DOE PAGES

Biernat, Elmar P.; Peña, M. T.; Ribeiro, J. E.; ...

2014-11-14

The π-π scattering amplitude calculated with a model for the quark-antiquark interaction in the framework of the Covariant Spectator Theory (CST) is shown to satisfy the Adler zero constraint imposed by chiral symmetry. The CST formalism is established in Minkowski space and our calculations are performed in momentum space. We prove that the axial-vector Ward-Takahashi identity is satisfied by our model. Then we show that, similarly to what happens within the Bethe-Salpeter formalism, application of the axial-vector Ward Takahashi identity to the CST π-π scattering amplitude allows us to sum the intermediate quark-quark interactions to all orders. Thus, the Adlermore » self-consistency zero for π-π scattering in the chiral limit emerges as the result for this sum.« less

Controlling Chirality of Entropic Crystals.

PubMed

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

2015-10-09

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

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.

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

PubMed

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

2013-01-01

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

Molecular-Level Design of Heterogeneous Chiral Catalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 formingmore » 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

Auxiliary-field quantum Monte Carlo simulations of neutron matter in chiral effective field theory.

PubMed

Wlazłowski, G; Holt, J W; Moroz, S; Bulgac, A; Roche, K J

2014-10-31

We present variational Monte Carlo calculations of the neutron matter equation of state using chiral nuclear forces. The ground-state wave function of neutron matter, containing nonperturbative many-body correlations, is obtained from auxiliary-field quantum Monte Carlo simulations of up to about 340 neutrons interacting on a 10(3) discretized lattice. The evolution Hamiltonian is chosen to be attractive and spin independent in order to avoid the fermion sign problem and is constructed to best reproduce broad features of the chiral nuclear force. This is facilitated by choosing a lattice spacing of 1.5 fm, corresponding to a momentum-space cutoff of Λ=414  MeV/c, a resolution scale at which strongly repulsive features of nuclear two-body forces are suppressed. Differences between the evolution potential and the full chiral nuclear interaction (Entem and Machleidt Λ=414  MeV [L. Coraggio et al., Phys. Rev. C 87, 014322 (2013).

Self-organization of atoms coupled to a chiral reservoir

NASA Astrophysics Data System (ADS)

Eldredge, Zachary; Jarzynski, Christopher; Chang, Darrick; Gorshkov, Alexey

2016-05-01

Tightly confined modes of light, as in optical nanofibers or photonics crystal waveguides, can lead to large optical coupling in atomic systems, which mediates long-range interactions between atoms. These one-dimensional systems can naturally possess couplings which are asymmetric between modes in different directions. In this poster, we examine the self-organizing behavior of atoms in one dimension coupled to a chiral reservoir. We determine the behavior of the self-organized solution to the equations of motion in different parameter regimes, relative to both the detuning of the pump laser and the degree of reservoir chirality. In addition to the spatial configuration of self-organized atoms, we calculate possible experimental signatures.

Spin chirality and polarised neutron scattering

NASA Astrophysics Data System (ADS)

Plakhty, V. P.; Maleyev, S. V.; Kulda, J.; Visser, E. D.; Wosnitza, J.; Moskvin, E. V.; Brückel, Th.; Kremer, R. K.

2001-03-01

Possibilities of polarised neutrons in studies of chiral criticality are discussed. The critical exponents β C of the average chirality below TN, as well as φ C=β C+γ C and, therefore, γ C of the chiral susceptibility above TN are determined for a XY triangular lattice antiferromagnet (TLA) CsMnBr3: β C=0.44(2) , γ C=0.84(7) . The critical behaviour of the chirality that orders at TN with a relative precision of 5×10 -4 proves that the phase transition belongs to a new chiral universality class. For the TLA CsNiCl 3 ( S=1) we found in the XY region ( B=3 T) φ C=1.24(7) in agreement with the Monte-Carlo value φ C=1.22(6) for the chiral universality class. In the easy-axis region at B=1 T, φ C=0.54(4) , and the Haldane excitations are observed in the polarisation-dependent inelastic cross section above TN. The helimagnet holmium exhibits a different chiral criticality with φ C=1.56(5) , essentially higher than for TLAs.

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.

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.

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

NASA Astrophysics Data System (ADS)

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

2015-08-01

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

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

Deterministic photon-emitter coupling in chiral photonic circuits.

PubMed

Söllner, Immo; Mahmoodian, Sahand; Hansen, Sofie Lindskov; Midolo, Leonardo; Javadi, Alisa; Kiršanskė, Gabija; Pregnolato, Tommaso; El-Ella, Haitham; Lee, Eun Hye; Song, Jin Dong; Stobbe, Søren; Lodahl, Peter

2015-09-01

Engineering photon emission and scattering is central to modern photonics applications ranging from light harvesting to quantum-information processing. To this end, nanophotonic waveguides are well suited as they confine photons to a one-dimensional geometry and thereby increase the light-matter interaction. In a regular waveguide, a quantum emitter interacts equally with photons in either of the two propagation directions. This symmetry is violated in nanophotonic structures in which non-transversal local electric-field components imply that photon emission and scattering may become directional. Here we show that the helicity of the optical transition of a quantum emitter determines the direction of single-photon emission in a specially engineered photonic-crystal waveguide. We observe single-photon emission into the waveguide with a directionality that exceeds 90% under conditions in which practically all the emitted photons are coupled to the waveguide. The chiral light-matter interaction enables deterministic and highly directional photon emission for experimentally achievable on-chip non-reciprocal photonic elements. These may serve as key building blocks for single-photon optical diodes, transistors and deterministic quantum gates. Furthermore, chiral photonic circuits allow the dissipative preparation of entangled states of multiple emitters for experimentally achievable parameters, may lead to novel topological photon states and could be applied for directional steering of light.

Deterministic photon-emitter coupling in chiral photonic circuits

NASA Astrophysics Data System (ADS)

Söllner, Immo; Mahmoodian, Sahand; Hansen, Sofie Lindskov; Midolo, Leonardo; Javadi, Alisa; Kiršanskė, Gabija; Pregnolato, Tommaso; El-Ella, Haitham; Lee, Eun Hye; Song, Jin Dong; Stobbe, Søren; Lodahl, Peter

2015-09-01

Engineering photon emission and scattering is central to modern photonics applications ranging from light harvesting to quantum-information processing. To this end, nanophotonic waveguides are well suited as they confine photons to a one-dimensional geometry and thereby increase the light-matter interaction. In a regular waveguide, a quantum emitter interacts equally with photons in either of the two propagation directions. This symmetry is violated in nanophotonic structures in which non-transversal local electric-field components imply that photon emission and scattering may become directional. Here we show that the helicity of the optical transition of a quantum emitter determines the direction of single-photon emission in a specially engineered photonic-crystal waveguide. We observe single-photon emission into the waveguide with a directionality that exceeds 90% under conditions in which practically all the emitted photons are coupled to the waveguide. The chiral light-matter interaction enables deterministic and highly directional photon emission for experimentally achievable on-chip non-reciprocal photonic elements. These may serve as key building blocks for single-photon optical diodes, transistors and deterministic quantum gates. Furthermore, chiral photonic circuits allow the dissipative preparation of entangled states of multiple emitters for experimentally achievable parameters, may lead to novel topological photon states and could be applied for directional steering of light.

Laser R2PI spectroscopic and mass spectrometric studies of chiral neurotransmitters

NASA Astrophysics Data System (ADS)

Giardini, A.; Marotta, V.; Paladini, A.; Piccirillo, S.; Rondino, F.; Satta, M.; Speranza, M.

2007-07-01

One color, mass selected resonant two-photon ionization (1cR2PI) spectra of supersonically expanded bare neurotransmitter, (1 S,2 S)-(+)- N-methyl pseudoephedrine (MPE), and its complexes with chiral and achiral molecules have been investigated. The excitation spectrum of bare MPE has been analyzed and discussed on the basis of theoretical predictions at the B3LYP/6-31G** level of theory. The results allowed to get information on the possible conformers of MPE molecule and on the intermolecular forces on its cluster formed with a variety of solvent molecules, including chiral alcohols, lactates and water. Further information on intermolecular interactions have been obtained with ESI-CID-MS 2 technique, applied to chiral biomolecules linked through a metal ion to the neurotransmitter. The experimental results are compared with theoretical predictions.

Out-of-plane chiral domain wall spin-structures in ultrathin in-plane magnets

DOE PAGES

Chen, Gong; Kang, Sang Pyo; Ophus, Colin; ...

2017-05-19

Chiral spin textures in ultrathin films, such as skyrmions or chiral domain walls, are believed to offer large performance advantages in the development of novel spintronics technologies. While in-plane magnetized films have been studied extensively as media for current- and field-driven domain wall dynamics with applications in memory or logic devices, the stabilization of chiral spin textures in in-plane magnetized films has remained rare. Here we report a phase of spin structures in an in-plane magnetized ultrathin film system where out-of-plane spin orientations within domain walls are stable. Moreover, while domain walls in in-plane films are generally expected to bemore » non-chiral, we show that right-handed spin rotations are strongly favoured in this system, due to the presence of the interfacial Dzyaloshinskii-Moriya interaction. These results constitute a platform to explore unconventional spin dynamics and topological phenomena that may enable high-performance in-plane spin-orbitronics devices.« less

Impact of pyrrolidine-bispyrrole DNA minor groove binding agents and chirality on global proteomic profile in Escherichia Coli.

PubMed

Yang, Ya-Ting; Lin, Chun-Yu; Jeng, Jingyueh; Ong, Chi-Wi

2013-05-23

There is great interest in the design of small molecules that selectively target minor grooves of duplex DNA for controlling specific gene expression implicated in a disease. The design of chiral small molecules for rational drug design has attracted increasing attention due to the chirality of DNA. Yet, there is limited research on the chirality effect of minor groove binders on DNA interaction, especially at the protein expression level. This paper is an attempt to illustrate that DNA binding affinity might not provide a full picture on the biological activities. Drug interacting at the genomic level can be translated to the proteomic level. Here we have illustrated that although the chiral bispyrrole-pyrrolidine-oligoamides, PySSPy and PyRSPy, showed low binding affinity to DNA, their influence at the proteomic level is significant. More importantly, the chirality also plays a role. Two-dimensional proteomic profile to identify the differentially expressed protein in Escherichia coli DH5α (E coli DH5α) were investigated. E coli DH5α incubated with the chiral PySSPy and PyRSPy, diastereomeric at the pyrrolidine ring, showed differential expression of eighteen proteins as observed through two dimensional proteomic profiling. These eighteen proteins identified by MALDI_TOF/TOF MS include antioxidant defense, DNA protection, protein synthesis, chaperone, and stress response proteins. No statistically significant toxicity was observed at the tested drug concentrations as measured via MTT assay. The current results showed that the chiral PySSPy and PyRSPy impact on the proteomic profiling of E coli DH5α, implicating the importance of drug chirality on biological activities at the molecular level.

Chirally directed formation of nanometer-scale proline clusters.

PubMed

Myung, Sunnie; Fioroni, Marco; Julian, Ryan R; Koeniger, Stormy L; Baik, Mu-Hyun; Clemmer, David E

2006-08-23

Ion mobility measurements, combined with molecular mechanics simulations, are used to study enantiopure and racemic proline clusters formed by electrospray ionization. Broad distributions of cluster sizes and charge states are observed, ranging from clusters containing only a few proline units to clusters that contain more than 100 proline units (i.e., protonated clusters of the form [xPro + nH](n+) with x = 1 to >100 and n = 1-7). As the sizes of clusters increase, there is direct evidence for nanometer scale, chirally induced organization into specific structures. For n = 4 and 5, enantiopure clusters of approximately 50 to 100 prolines assemble into structures that are more elongated than the most compact structure that is observed from the racemic proline clusters. A molecular analogue, cis-4-hydroxy-proline, displays significantly different behavior, indicating that in addition to the rigidity of the side chain ring, intermolecular interactions are important in the formation of chirally directed clusters. This is the first case in which assemblies of chirally selective elongated structures are observed in this size range of amino acid clusters. Relationships between enantiopurity, cluster shape, and overall energetics are discussed.

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. © 2013 Wiley Periodicals, Inc.

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

PubMed

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

2017-09-15

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

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

PubMed

Choi, Suk-Won; Takezoe, Hideo

2016-09-28

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

Structure of neutron star crusts from new Skyrme effective interactions constrained by chiral effective field theory

NASA Astrophysics Data System (ADS)

Lim, Yeunhwan; Holt, Jeremy W.

2017-06-01

We investigate the structure of neutron star crusts, including the crust-core boundary, based on new Skyrme mean field models constrained by the bulk-matter equation of state from chiral effective field theory and the ground-state energies of doubly-magic nuclei. Nuclear pasta phases are studied using both the liquid drop model as well as the Thomas-Fermi approximation. We compare the energy per nucleon for each geometry (spherical nuclei, cylindrical nuclei, nuclear slabs, cylindrical holes, and spherical holes) to obtain the ground state phase as a function of density. We find that the size of the Wigner-Seitz cell depends strongly on the model parameters, especially the coefficients of the density gradient interaction terms. We employ also the thermodynamic instability method to check the validity of the numerical solutions based on energy comparisons.

Amino Acid Chiral Selection Via Weak Interactions in Stellar Environments: Implications for the Origin of Life.

PubMed

Famiano, Michael A; Boyd, Richard N; Kajino, Toshitaka; Onaka, Takashi; Mo, Yirong

2018-06-11

Magnetochiral phenomena may be responsible for the selection of chiral states of biomolecules in meteoric environments. For example, the Supernova Amino Acid Processing (SNAAP) Model was proposed previously as a possible mode of magnetochiral selection of amino acids by way of the weak interaction in strong magnetic fields. In earlier work, this model was shown to produce an enantiomeric excess (ee) as high as 0.014% for alanine. In this paper we present the results of molecular quantum chemistry calculations from which ees are determined for the α-amino acids plus isovaline and norvaline, which were found to have positive ees in meteorites. Calculations are performed for both isolated and aqueous states. In some cases, the aqueous state was found to produce larger ees reaching values as high as a few percent under plausible conditions.

No chiral truncation of quantum log gravity?

NASA Astrophysics Data System (ADS)

Andrade, Tomás; Marolf, Donald

2010-03-01

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

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

PubMed

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

2018-03-07

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

Amino acid ionic liquids as chiral ligands in ligand-exchange chiral separations.

PubMed

Liu, Qian; Wu, Kangkang; Tang, Fei; Yao, Lihua; Yang, Fei; Nie, Zhou; Yao, Shouzhuo

2009-09-28

Recently, amino acid ionic liquids (AAILs) have attracted much research interest. In this paper, we present the first application of AAILs in chiral separation based on the chiral ligand exchange principle. By using 1-alkyl-3-methylimidazolium L-proline (L-Pro) as a chiral ligand coordinated with copper(II), four pairs of underivatized amino acid enantiomers-dl-phenylalanine (dl-Phe), dl-histidine (dl-His), dl-tryptophane (dl-Trp), and dl-tyrosine (dl-Tyr)-were successfully separated in two major chiral separation techniques, HPLC and capillary electrophoresis (CE), with higher enantioselectivity than conventionally used amino acid ligands (resolution (R(s))=3.26-10.81 for HPLC; R(s)=1.34-4.27 for CE). Interestingly, increasing the alkyl chain length of the AAIL cation remarkably enhanced the enantioselectivity. It was inferred that the alkylmethylimidazolium cations and L-Pro form ion pairs on the surface of the stationary phase or on the inner surface of the capillary. The ternary copper complexes with L-Pro are consequently attached to the support surface, thus inducing an ion-exchange type of retention for the dl-enantiomers. Therefore, the AAIL cation plays an essential role in the separation. This work demonstrates that AAILs are good alternatives to conventional amino acid ligands for ligand-exchange-based chiral separation. It also reveals the tremendous application potential of this new type of task-specific ILs.

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

NASA Astrophysics Data System (ADS)

Mueller, Niklas; Venugopalan, Raju

2018-03-01

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

Chiral Superstructure Mesophases of Achiral Bent-Shaped Molecules - Hierarchical Chirality Amplification and Physical Properties.

PubMed

Le, Khoa V; Takezoe, Hideo; Araoka, Fumito

2017-07-01

Chiral mesophases in achiral bent-shaped molecules have attracted particular attention since their discovery in the middle 1990s, not only because of their homochirality and polarity, but also due to their unique physical/physicochemical properties. Here, the most intriguing results in the studies of such symmetry-broken states, mainly helical-nanofilament (HNF) and dark-conglomerate (DC) phases, are reviewed. Firstly, basic information on the typical appearance and optical activity in these phases is introduced. In the following section, the formation of mesoscopic chiral superstructures in the HNF and DC phases is discussed in terms of hierarchical chirality. Nanoscale phase segregation in mixture systems and gelation ability in the HNF phase are also described. In addition, some other related chiral phases of bent-shaped molecules are shown. Recent attempts to control such mesoscopic chiral structure and the alignment/confinement of HNFs are also discussed, along with several examples of their fascinating advanced physical properties, i.e. huge enhancement of circular dichroism, electro- and photo-tunable optical activities, chirality-induced nonlinear optics (second-harmonic-generation circular difference and electrogyration effect), enhanced hydrophobicity through the dual-scale surface morphological modulation, and photoconductivity in the HNF/fullerene binary system. Future prospects from basic science and application viewpoints are also indicated in the concluding section. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Molecular chirality: language, history, and significance.

PubMed

Gal, Joseph

2013-01-01

In this chapter some background material concerning molecular chirality and enantiomerism is presented. First some basic chemical-molecular aspects of chirality are reviewed, after which certain relevant terminology whose use in the literature has been problematic is discussed. Then an overview is provided of some of the early discoveries that laid the foundations of the science of molecular chirality in chemistry and biology, including the discovery of the phenomenon of molecular chirality by L. Pasteur, the proposals for the asymmetric carbon atom by J.H. van 't Hoff and J.A. Lebel, Pasteur's discovery of biological enantioselectivity, the discovery of enantioselectivity at biological receptors by A. Piutti, the studies of enzymatic stereoselectivity by E. Fischer, and the work on enantioselectivity in pharmacology by A. Cushny. Finally, the role of molecular chirality in pharmacotherapy and new-drug development, arguably one of the main driving forces for the current intense interest in the phenomenon of molecular chirality, is discussed.

Stable Pentaquarks from Strange Chiral Multiplets

DOE Office of Scientific and Technical Information (OSTI.GOV)

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.more » 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.« less

The effect of fenoterol stereochemistry on the β2 adrenergic receptor system: ligand directed chiral recognition

PubMed Central

Jozwiak, Krzysztof; Plazinska, Anita; Toll, Lawrence; Jimenez, Lucita; Woo, Anthony Yiu-Ho; Xiao, Rui-Ping; Wainer, Irving W.

2011-01-01

The β2 adrenergic receptor (β2-AR) is a model system for studying the ligand recognition process in G-protein coupled receptors. Fenoterol (FEN) is a β2-AR selective agonist that has two centers of chirality and exists as four stereoisomers. Radioligand binding studies determined that stereochemistry greatly influences the binding affinity. Subsequent Van’t Hoff analysis shows very different thermodynamics of binding depending on the stereoconfiguration of the molecule. The binding of (S,x’)-isomers is almost entirely enthalpy controlled whereas binding of (R,x’)-isomers is purely entropy driven. Stereochemistry of FEN molecule also affects the coupling of the receptor to different G proteins. In a rat cardiomyocyte contractility model, (R,R’)-FEN was shown to selectively activate Gs protein signaling while the (S,R’)- isomer activated both Gi and Gs protein. The overall data demonstrate that the chirality at the two chiral centers of the FEN molecule influences the magnitude of binding affinity, thermodynamics of local interactions within the binding site and the global mechanism of β2-AR activation. Differences in thermodynamic parameters and non-uniform G-protein coupling suggest a mechanism of chiral recognition in which observed enantioselectivities arise from the interaction of the (R,x’)-FEN stereoisomers with a different receptor conformation than the one with which the (S,x’)-isomer interacts. PMID:21618615

Chiral bobbers and skyrmions in epitaxial FeGe/Si(111) films

NASA Astrophysics Data System (ADS)

Ahmed, Adam S.; Rowland, James; Esser, Bryan D.; Dunsiger, Sarah R.; McComb, David W.; Randeria, Mohit; Kawakami, Roland K.

2018-04-01

We report experimental and theoretical evidence for the formation of chiral bobbers—an interfacial topological spin texture—in FeGe films grown by molecular beam epitaxy. After establishing the presence of skyrmions in FeGe/Si(111) thin-film samples through Lorentz transmission electron microscopy and the topological Hall effect, we perform magnetization measurements that reveal an inverse relationship between the film thickness and the slope of the susceptibility (d χ /d H ). We present evidence for the evolution as a function of film thickness L from a skyrmion phase for L chiral bobbers at the interface for L >LD/2 , where LD˜70 nm is the FeGe pitch length. We show using micromagnetic simulations that chiral bobbers, earlier predicted to be metastable, are in fact the stable ground state in the presence of an additional interfacial Rashba Dzyaloshinskii-Moriya interaction.

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.

Chiral Symmetry Breaking and Complete Chiral Purity by Thermodynamic-Kinetic Feedback Near Equilibrium: Implications for the Origin of Biochirality

NASA Astrophysics Data System (ADS)

Viedma, Cristobal

2007-05-01

Chiral symmetry breaking occurs when a physical or chemical process spontaneously generates a large excess of one of the two enantiomers-left-handed (L) or right-handed (D)--with no preference as to which of the two enantiomers is produced. From the viewpoint of energy, these two enantiomers can exist with an equal probability, and inorganic processes that involve chiral products commonly yield a racemic mixture of both. The fact that biologically relevant molecules exist only as one of the two enantiomers is a fascinating example of complete symmetry breaking in chirality and has long intrigued the science community. The origin of this selective chirality has remained a fundamental enigma with regard to the origin of life since the time of Pasteur, some 140 years ago. Here, it is shown that two populations of chiral 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 the course of the common process of growth-dissolution. This unexpected chiral symmetry breaking can be explained by the feedback between the thermodynamic control of dissolution and the kinetics of the growth process near equilibrium. This ``thermodynamic-kinetic feedback near equilibrium'' is established as a mechanism to achieve complete chiral purity in solid state from a previously solid racemic medium. The way in which this mechanism could operate in solutions of chiral biomolecules is described. Finally, based on this mechanism, experiments designed to search for chiral purity in a new way are proposed: chiral purity of amino acids or biopolymers is predicted in solid phase from a previously solid racemic medium. This process may have played a key role in the origin of biochirality.

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.

Surface Chirality of Gly-Pro Dipeptide Adsorbed on a Cu(110) Surface.

PubMed

Cruguel, Hervé; Méthivier, Christophe; Pradier, Claire-Marie; Humblot, Vincent

2015-07-01

The adsorption of chiral Gly-Pro dipeptide on Cu(110) has been characterized by combining in situ polarization modulation infrared reflection absorption spectroscopy (PM-RAIRS) and X-ray photoelectron spectroscopy (XPS). The chemical state of the dipeptide, and its anchoring points and adsorption geometry, were determined at various coverage values. Gly-Pro molecules are present on Cu(110) in their anionic form (NH2 /COO(-)) and adsorb under a 3-point binding via both oxygen atoms of the carboxylate group and via the nitrogen atom of the amine group. Low-energy electron diffraction (LEED) and scanning tunneling microscopy (STM) have shown the presence of an extended 2D chiral array, sustained via intermolecular H-bonds interactions. Furthermore, due to the particular shape of the molecule, only one homochiral domain is formed, creating thus a truly chiral surface. © 2015 Wiley Periodicals, Inc.

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

PubMed Central

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

2018-01-01

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

Some recent experimental results related to nuclear chirality

NASA Astrophysics Data System (ADS)

Timár, J.; Kuti, I.; Sohler, D.; Starosta, K.; Koike, T.; Paul, E. S.

2014-09-01

Detailed band structures of three chiral-candidate nuclei, 134Pr, 132La and 103Rh have been studied. The aim of the study was twofold. First, to try to explore the reasons behind the contradiction between the theoretically predicted chirality in these nuclei and the recently observed fingerprints that suggest non-chiral interpretation for the previous chiral candidate band doublets. Second, to search for multiple chiral bands of different types in these nuclei. In 134Pr a new πh11/2vh11/2 band has been observed besides the previously known chiral-candidate πh11/2vh11/2 doublet. This new band and the yrare πh11/2vh11/2 band show the expected features of a chiral doublet structure. This fact combined with the observed similarity between the band structures of 134Pr and 132La suggests that chirality might exist in these nuclei. The detailed study of the 103Rh band structure resulted in the observation of two new chiral-doublet looking structures besides the previously known one. This is indicative of possible existence of multiple chiral doublet structure in this nucleus.

Chiralities of spiral waves and their transitions.

PubMed

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

2013-06-01

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

Effects of Fluctuations on Inhomogeneous Chiral Transitions

NASA Astrophysics Data System (ADS)

Lee, Tong-Gyu; Yoshiike, Ryo; Tatsumi, Toshitaka

We discuss the features of the order-parameter fluctuations in the normal phase near the phase boundary and their effects on the phase transition from the normal to the inhomogeneous phase with spatially modulated order parameter. Focusing on the chiral symmetry breaking, i.e., inhomogeneous chiral transition, we consider the fluctuation of the chiral pair consisting of quark-antiquark or quark-hole pair within the two-flavor Nambu-Jona-Lasinio model in the chiral limit. We clarify the roles of quantum and thermal fluctuations and also argue that anomalies for thermodynamic quantities in the inhomogeneous chiral transition should lead to phenomenological implications.

Adsorption of lactic acid on chiral Pt surfaces—A density functional theory study

NASA Astrophysics Data System (ADS)

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

2013-02-01

The adsorption of the chiral molecule lactic acid on chiral Pt surfaces is studied by density functional theory calculations. First, we study the adsorption of L-lactic acid on the flat Pt(111) surface. Using the optimed PBE - van der Waals (oPBE-vdW) functional, which includes van der Waals forces on an ab initio level, it is shown that the molecule has two binding sites, a carboxyl and the hydroxyl oxygen atoms. Since real chiral surfaces are (i) known to undergo thermal roughening that alters the distribution of kinks and step edges but not the overall chirality and (ii) kink sites and edge sites are usually the energetically most favored adsorption sites, we focus on two surfaces that allow qualitative sampling of the most probable adsorption sites. We hereby consider chiral surfaces exhibiting (111) facets, in particular, Pt(321) and Pt(643). The binding sites are either both on kink sites—which is the case for Pt(321) or on one kink site—as on Pt(643). The binding energy of the molecule on the chiral surfaces is much higher than on the Pt(111) surface. We show that the carboxyl group interacts more strongly than the hydroxyl group with the kink sites. The results indicate the possible existence of very small chiral selectivities of the order of 20 meV for the Pt(321) and Pt(643) surfaces. L-lactic acid is more stable on Pt(321)S than D-lactic acid, while the chiral selectivity is inverted on Pt(643)S. The most stable adsorption configurations of L- and D-lactic acid are similar for Pt(321) but differ for Pt(643). We explore the impact of the different adsorption geometries on the work function, which is important for field ion microscopy.

Chiral vortical effect generated by chiral anomaly in vortex-skyrmions

NASA Astrophysics Data System (ADS)

Volovik, G. E.

2017-03-01

We discuss the type of the general macroscopic parity-violating effects, when there is the current along the vortex, which is concentrated in the vortex core. We consider vortices in chiral superfluids with Weyl points. In the vortex core, the positions of the Weyl points form the skyrmion structure. We show that the mass current concentrated in such a core is provided by the spectral flow through the Weyl points according to the Adler-Bell-Jackiw equation for chiral anomaly.

Chiral ionic liquids in chromatographic and electrophoretic separations.

PubMed

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

2014-10-10

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

Chiral pesticides: identification, description, and environmental implications.

PubMed

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

2012-01-01

Of the 1,693 pesticides considered in this review, 1,594 are organic chemicals, 47 are inorganic chemicals, 53 are of biological origin (largely non chemical; insect,fungus, bacteria, virus, etc.), and 2 have an undetermined structure. Considering that the EPA's Office of Pesticide Programs found 1,252 pesticide active ingredients(EPA Pesticides Customer Service 2011), we consider this dataset to be comprehensive; however, no direct comparison of the compound lists was undertaken. Of all pesticides reviewed, 482 (28%) are chiral; 30% are chiral when considering only the organic chemical pesticides. A graph of this distribution is shown in Fig. 7a. Each pesticide is classified with up to three pesticidal utilities (e.g., fungicide, plant growth regulator, rodenticide, etc.), taken first from the Pesticide Manual as a primary source, and the Compendium of Common Pesticide Names website as a secondary source. Of the chiral pesticides, 195 (34%) are insecticides (including attractants, pheromones, and repellents), 150 (27%) are herbicides (including plant growth regulators and herbicide safeners), 104 (18%) are fungicides, and 55 (10%)are acaricides. The distribution of chiral pesticides by utility is shown in Fig. 7b,including categories of pesticides that make up 3%t or less of the usage categories.Figure 7c shows a similar distribution of non chiral pesticide usage categories. Of the chiral pesticides, 270 (56%) have one chiral feature, 105 (22%) have two chiral features, 30 (6.2%) have three chiral features, and 29 (6.0%) have ten or more chiral features.Chiral chemicals pose many difficulties in stereospecific synthesis, characterization, and analysis. When these compounds are purposely put into the environment,even more interesting complications arise in tracking, monitoring, and predicting their fate and risks. More than 475 pesticides are chiral, as are other chiral contaminants such as pharmaceuticals, polychlorinated biphenyls, brominated flame retardants

Chiral corrections to the Adler-Weisberger sum rule

NASA Astrophysics Data System (ADS)

Beane, Silas R.; Klco, Natalie

2016-12-01

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

Coherent neutrinoproduction of photons and pions in a chiral effective field theory for nuclei

NASA Astrophysics Data System (ADS)

Zhang, Xilin; Serot, Brian D.

2012-09-01

Background: The neutrinoproduction of photons and pions from nucleons and nuclei is relevant to the background analysis in neutrino-oscillation experiments [for example, the MiniBooNE; MiniBooNE Collaboration, A. A. Aquilar-Arevalo , Phys. Rev. Lett.0031-900710.1103/PhysRevLett.100.032301 100, 032301 (2008)]. The production from nucleons and incoherent production with Eν⩽0.5GeV have been studied in B. D. Serot and X. Zhang, Phys. Rev. CPRVCAN0556-281310.1103/PhysRevC.86.015501 86, 015501 (2012); and X. Zhang and B. D. Serot, Phys. Rev. C1110-865710.1103/PhysRevC.86.035502 86, 035502 (2012).Purpose: Study coherent productions with Eν⩽0.5GeV. Also address the contributions of two contact terms in neutral current (NC) photon production that are partially related to the proposed anomalous ω(ρ), Z boson, and photon interactions.Methods: We work in the framework of a Lorentz-covariant effective field theory (EFT), which contains nucleons, pions, the Δ (1232) (Δs), isoscalar scalar (σ) and vector (ω) fields, and isovector vector (ρ) fields, and incorporates a nonlinear realization of (approximate) SU(2)L⊗SU(2)R chiral symmetry. A revised version of the so-called “optimal approximation” is applied, where one-nucleon interaction amplitude is factorized out and the medium-modifications and pion wave function distortion are included. The calculation is tested against the coherent pion photoproduction data.Results: The computation shows an agreement with the pion photoproduction data, although precisely determining the Δ modification is entangled with one mentioned contact term. The uncertainty in the Δ modification leads to uncertainties in both pion and photon neutrinoproductions. In addition, the contact term plays a significant role in NC photon production.Conclusions: First, the contact term increases NC photon production by ˜10% assuming a reasonable range of the contact coupling, which however seems not significant enough to explain the Mini

Optical activity of chirally distorted nanocrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tepliakov, Nikita V.; Baimuratov, Anvar S.; Baranov, Alexander V.

2016-05-21

We develop a general theory of optical activity of semiconductor nanocrystals whose chirality is induced by a small perturbation of their otherwise achiral electronic subsystems. The optical activity is described using the quantum-mechanical expressions for the rotatory strengths and dissymmetry factors introduced by Rosenfeld. We show that the rotatory strengths of optically active transitions are decomposed on electric dipole and magnetic dipole contributions, which correspond to the electric dipole and magnetic dipole transitions between the unperturbed quantum states. Remarkably, while the two kinds of rotatory strengths are of the same order of magnitude, the corresponding dissymmetry factors can differ bymore » a factor of 10{sup 5}. By maximizing the dissymmetry of magnetic dipole absorption one can significantly enhance the enantioselectivity in the interaction of semiconductor nanocrystals with circularly polarized light. This feature may advance chiral and analytical methods, which will benefit biophysics, chemistry, and pharmaceutical science. The developed theory is illustrated by an example of intraband transitions inside a semiconductor nanocuboid, whose rotatory strengths and dissymmetry factors are calculated analytically.« less

Optical activity of chirally distorted nanocrystals

NASA Astrophysics Data System (ADS)

Tepliakov, Nikita V.; Baimuratov, Anvar S.; Baranov, Alexander V.; Fedorov, Anatoly V.; Rukhlenko, Ivan D.

2016-05-01

We develop a general theory of optical activity of semiconductor nanocrystals whose chirality is induced by a small perturbation of their otherwise achiral electronic subsystems. The optical activity is described using the quantum-mechanical expressions for the rotatory strengths and dissymmetry factors introduced by Rosenfeld. We show that the rotatory strengths of optically active transitions are decomposed on electric dipole and magnetic dipole contributions, which correspond to the electric dipole and magnetic dipole transitions between the unperturbed quantum states. Remarkably, while the two kinds of rotatory strengths are of the same order of magnitude, the corresponding dissymmetry factors can differ by a factor of 105. By maximizing the dissymmetry of magnetic dipole absorption one can significantly enhance the enantioselectivity in the interaction of semiconductor nanocrystals with circularly polarized light. This feature may advance chiral and analytical methods, which will benefit biophysics, chemistry, and pharmaceutical science. The developed theory is illustrated by an example of intraband transitions inside a semiconductor nanocuboid, whose rotatory strengths and dissymmetry factors are calculated analytically.

Chiral discrimination in nuclear magnetic resonance spectroscopy

NASA Astrophysics Data System (ADS)

Lazzeretti, Paolo

2017-11-01

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

Chiral magnetic effect in condensed matter systems

DOE PAGES

Li, Qiang; Kharzeev, Dmitri E.

2016-12-01

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

Left-right asymmetry is formed in individual cells by intrinsic cell chirality.

PubMed

Hatori, Ryo; Ando, Tadashi; Sasamura, Takeshi; Nakazawa, Naotaka; Nakamura, Mitsutoshi; Taniguchi, Kiichiro; Hozumi, Shunya; Kikuta, Junichi; Ishii, Masaru; Matsuno, Kenji

2014-08-01

Many animals show left-right (LR) asymmetric morphology. The mechanisms of LR asymmetric development are evolutionarily divergent, and they remain elusive in invertebrates. Various organs in Drosophila melanogaster show stereotypic LR asymmetry, including the embryonic gut. The Drosophila embryonic hindgut twists 90° left-handedly, thereby generating directional LR asymmetry. We recently revealed that the hindgut epithelial cell is chiral in shape and other properties; this is termed planar cell chirality (PCC). We previously showed by computer modeling that PCC is sufficient to induce the hindgut rotation. In addition, both the PCC and the direction of hindgut twisting are reversed in Myosin31DF (Myo31DF) mutants. Myo31DF encodes Drosophila MyosinID, an actin-based motor protein, whose molecular functions in LR asymmetric development are largely unknown. Here, to understand how PCC directs the asymmetric cell-shape, we analyzed PCC in genetic mosaics composed of cells homozygous for mutant Myo31DF, some of which also overexpressed wild-type Myo31DF. Wild-type cell-shape chirality only formed in the Myo31DF-overexpressing cells, suggesting that cell-shape chirality was established in each cell and reflects intrinsic PCC. A computer model recapitulating the development of this genetic mosaic suggested that mechanical interactions between cells are required for the cell-shape behavior seen in vivo. Our mosaic analysis also suggested that during hindgut rotation in vivo, wild-type Myo31DF suppresses the elongation of cell boundaries, supporting the idea that cell-shape chirality is an intrinsic property determined in each cell. However, the amount and distribution of F-actin and Myosin II, which are known to help generate the contraction force on cell boundaries, did not show differences between Myo31DF mutant cells and wild-type cells, suggesting that the static amount and distribution of these proteins are not involved in the suppression of cell-boundary elongation

Enantiomeric-Enriched Ferrocenes: Synthesis, Chiral Resolution, and Mathematic Evaluation of CD-chiral Selector Energies with Ferrocene-Conjugates.

PubMed

Snegur, Lubov V; Borisov, Yurii A; Kuzmenko, Yuliya V; Davankov, Vadim A; Ilyin, Mikhail M; Ilyin, Mikhail M; Arhipov, Dmitry E; Korlyukov, Alexander A; Kiselev, Sergey S; Simenel, Alexander A

2017-08-25

Enantiomeric-enriched ferrocene-modified pyrazoles were synthesized via the reaction of the ferrocene alcohol, ( S )-FcCH(OH)CH₃ (Fc = ferrocenyl), with various pyrazoles in acidic conditions at room temperature within several minutes. X-ray structural data for racemic ( R , S )-1 N -(3,5-dimethyl pyrazolyl)ethyl ferrocene ( 1 ) and its ( S )-enantiomer ( S )- 1 were determined. A series of racemic pyrazolylalkyl ferrocenes was separated into enantiomers by analytical HPLC on β- and γ-cyclodextrins (CD) chiral stationary phases. The quantum chemical calculations of interaction energies of β-CD were carried out for both ( R )- and ( S )-enantiomers. A high correlation between experimental HPLC data and calculated interaction energies values was obtained.

Biomimetic Hierarchical Assembly of Helical Supraparticles from Chiral Nanoparticles

DOE PAGES

Zhou, Yunlong; Marson, Ryan L.; van Anders, Greg; ...

2016-02-22

Chiroptical materials found in butterflies, beetles, stomatopod crustaceans, and other creatures are attributed to biocomposites with helical motifs and multiscale hierarchical organization. These structurally sophisticated materials self-assemble from primitive nanoscale building blocks, a process that is simpler and more energy efficient than many top-down methods currently used to produce similarly sized three-dimensional materials. In this paper, we report that molecular-scale chirality of a CdTe nanoparticle surface can be translated to nanoscale helical assemblies, leading to chiroptical activity in the visible electromagnetic range. Chiral CdTe nanoparticles coated with cysteine self-organize around Te cores to produce helical supraparticles. D-/L-Form of the aminomore » acid determines the dominant left/right helicity of the supraparticles. Coarse-grained molecular dynamics simulations with a helical pair-potential confirm the assembly mechanism and the origin of its enantioselectivity, providing a framework for engineering three-dimensional chiral materials by self-assembly. Finally, the helical supraparticles further self-organize into lamellar crystals with liquid crystalline order, demonstrating the possibility of hierarchical organization and with multiple structural motifs and length scales determined by molecular-scale asymmetry of nanoparticle interactions.« less

Electric dipole moments of light nuclei from {chi}EFT

DOE Office of Scientific and Technical Information (OSTI.GOV)

Higa, Renato

I present recent calculations of EDMs of light nuclei using chiral effective field theory techniques. At leading-order, we argue that they can be expressed in terms of six CP-violating low-energy constants. With our expressions, eventual non-zero measurements of EDMs of deuteron, helion, and triton can be combined to disentangle the different sources of CP-violation.

Electric dipole moments of light nuclei from χEFT

NASA Astrophysics Data System (ADS)

Higa, Renato

2013-03-01

I present recent calculations of EDMs of light nuclei using chiral effective field theory techniques. At leading-order, we argue that they can be expressed in terms of six CP-violating low-energy constants. With our expressions, eventual non-zero measurements of EDMs of deuteron, helion, and triton can be combined to disentangle the different sources of CP-violation.

Chiral separation with gradient elution isotachophoresis for future in situ extraterrestrial analysis.

PubMed

Danger, Grégoire; Ross, David

2008-10-01

The first results of chiral separations with the gradient elution isotachophoresis method are presented. As previously described, citrate is used in the run buffer as the leading ion and borate in the sample buffer as the terminating ion. Modulation of parameters such as electrolyte pH, pressure scan rate, chiral selector concentration, combinations of CD or the percentage of ampholytes provides an easy optimization of the separations. To perform fluorescent detection 5-carboxyfluorescein succinimidyl ester and two fluorogenic-labeling agents, fluorescamine (Fluram) and 3-(4-carboxybenzoyl)quinoline-2-carboxaldehyde, are used to label amino acids. With the 5-carboxyfluorescein amino acids, chiral separations are easily obtained using a neutral CD ((2-hydroxypropyl)-beta-CD) at a low concentration (2 mmol/L). With Fluram amino acids, the situation is more complicated due to the formation of diastereoisomers and due to weak interactions with the different CDs used. The use of the 3-(4-carboxybenzoyl)quinoline-2-carboxaldehyde-labeling agent solves the problems observed with the Fluram agent while retaining the fluorogenic properties. These first results demonstrate the simplicity and the feasibility of gradient elution isotachophoresis for chiral separations.

Radical chiral Floquet phases in a periodically driven Kitaev model and beyond

NASA Astrophysics Data System (ADS)

Po, Hoi Chun; Fidkowski, Lukasz; Vishwanath, Ashvin; Potter, Andrew C.

2017-12-01

We theoretically discover a family of nonequilibrium fractional topological phases in which time-periodic driving of a 2D system produces excitations with fractional statistics, and produces chiral quantum channels that propagate a quantized fractional number of qubits along the sample edge during each driving period. These phases share some common features with fractional quantum Hall states, but are sharply distinct dynamical phenomena. Unlike the integer-valued invariant characterizing the equilibrium quantum Hall conductance, these phases are characterized by a dynamical topological invariant that is a square root of a rational number, inspiring the label: radical chiral Floquet phases. We construct solvable models of driven and interacting spin systems with these properties, and identify an unusual bulk-boundary correspondence between the chiral edge dynamics and bulk "anyon time-crystal" order characterized by dynamical transmutation of electric-charge into magnetic-flux excitations in the bulk.

Liquid crystal behavior induced assembling fabrication of conductive chiral MWCNTs@NCC nanopaper

NASA Astrophysics Data System (ADS)

Ren, Yumei; Wang, Tianjiao; Chen, Zhimin; Li, Jing; Tian, Qiuge; Yang, Hongxia; Xu, Qun

2016-11-01

The conductive chiral MWCNTs@NCC nanopapers obtained by the assembly of nanocrystalline cellulose liquid crystals (NCC LCs) host matrix along with one-dimensional (1-D) multi-walled carbon nanotubes (MWCNTs) have been studied in this work. Circular dichroism (CD) studies show strong signals stemming from the chiral nematic structure. Notably, the introduction of the MWCNTs has a pronounced effect on the chiral structure of the as-prepared nanopaper. Our experimental results indicate the multiple weak molecular interactions existing between MWCNTs and NCC are responsible for the effective dispersion and stabilization of MWCNTs. Moreover it also confirms the resulting nanopaper has an increased conductivity of 4.2 S/m at 1.96 wt% MWCNTs. So the co-assembly of the nanocomposite herein opens a gateway for preparing functional materials combining the photonic properties of the NCC LCs matrix with other building blocks that can supply other advantageous functions.

Chiral sp-orbital paired superfluid of fermionic atoms in a 2D spin-dependent optical lattice

NASA Astrophysics Data System (ADS)

Liu, Bo; Li, Xiaopeng; Wu, Biao; Liu, W. Vincent

2014-03-01

Recent progress in realizing synthetic quantum orbital materials in chequerboard and hexagonal optical lattices opens an avenue towards exploiting unconventional quantum states, advancing our understanding of correlated quantum matter. Here, we unveil a chiral sp -orbital paired superfluid state for an interacting two-component Fermi gas in a 2D spin-dependent optical lattice. Surprisingly, this novel state is found to exist in a wide regime of experimentally tunable interaction strengths. The coexistence of this chiral superfluid and the ferro-orbital order is reminiscent of that of magnetism and superconductivity which is a long-standing issue in condensed matter physics. The topological properties are demonstrated by the existence of gapless chiral fermions in the presence of domain wall defects, reminiscent of quantum Hall edge states. Such properties can be measured by radio frequency spectroscopy in cold atomic experiments. Work supported in part by U.S. ARO, AFOSR, and DARPA-OLE-ARO, Kaufman Foundation, and NSF of China.

Illuminating the chirality of Weyl fermions

NASA Astrophysics Data System (ADS)

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

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

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.

Induced chirality of cage metal complexes switched by their supramolecular and covalent binding.

PubMed

Kovalska, Vladyslava B; Vakarov, Serhii V; Kuperman, Marina V; Losytskyy, Mykhaylo Y; Gumienna-Kontecka, Elzbieta; Voloshin, Yan Z; Varzatskii, Oleg A

2018-01-23

An ability of the ribbed-functionalized iron(ii) clathrochelates to induce a CD output in interactions with a protein, covalent bonding or supramolecular interactions with a low-molecular-weight chiral inductor, was discovered. The interactions of CD inactive, carboxyl-terminated iron(ii) clathrochelates with serum albumin induced their molecular asymmetry, causing an appearance of strong CD signals in the range of 350-600 nm, whereas methyl ester and amide clathrochelate derivatives remained almost CD inactive. The CD spectra of carboxyl-terminated clathrochelates on supramolecular interactions or covalent bonding with (R)-(+)-1-phenylethylamine gave a substantially lower CD output than with albumin, affected by both the solvent polarity and the isomerism of clathrochelate's ribbed substituents. In supramolecular assemblies, the bands were most intensive for ortho-substituted carboxyl-terminated clathrochelates. The ortho- and meta-phenylethylamide cage complexes in tetrachloromethane inverted the signs of their CD bands compared with those in acetonitrile. It was suggested that the tris-dioximate metal clathrochelates possess a Russian doll-like molecular system. Because of the distorted TP-TAP geometry, their coordination polyhedron had no inversion centre and possessed an inherent chirality together with the equiprobability of its left(Λ)- and right(Δ)-handle twists. The selective fixation of one of these C 3 -distorted conformations resulted in the appearance of the CD signal in the range of their visible metal-to-ligand charge transfer bands. Calculations by DFT methods were used to illustrate the possible conformations of the macrobicyclic molecules, as well as the intramolecular interactions between the cage framework and optically active distal substituents responsible for the chirality induction of the metal-centred coordination polyhedra.

Enantioselective recognition at mesoporous chiral metal surfaces.

PubMed

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.

Chiral discrimination in diastereomeric salts of chlorine-substituted mandelic acid and phenylethylamine.

PubMed

He, Quan; Gomaa, Hassan; Rohani, Sohrab; Zhu, Jesse; Jennings, Michael

2010-08-01

The crystal structures of diastereomeric salts of chloromandelic acid and phenylethylamine were determined and are presented herein. The structure comparison between less soluble salts and more soluble salts shows that weak interactions such as CH/pi interactions and van der Waals gain importance and contribute to chiral recognition when the hydrogen bonding patterns are very similar. Copyright 2010 Wiley-Liss, Inc.

One-loop perturbative coupling of A and A⊙ through the chiral overlap operator

NASA Astrophysics Data System (ADS)

Makino, Hiroki; Morikawa, Okuto; Suzuki, Hiroshi

2017-06-01

We study the one-loop effective action defined by the chiral overlap operator in the four-dimensional lattice formulation of chiral gauge theories by Grabowska and Kaplan. In the tree-level continuum limit, the left-handed component of the fermion is coupled only to the original gauge field A, while the right-handed one is coupled only to A_\\star, which is given by the gradient flow of A with infinite flow time. In this paper, we show that the continuum limit of the one-loop effective action contains local interaction terms between A and A_\\star, which do not generally vanish even if the gauge representation of the fermion is anomaly free. We argue that the presence of such interaction terms can be regarded as undesired gauge symmetry-breaking effects in the formulation.

Surface-anchored poly(acryloyl-L(D)-valine) with enhanced chirality-selective effect on cellular uptake of gold nanoparticles

PubMed Central

Deng, Jun; Wu, Sai; Yao, Mengyun; Gao, Changyou

2016-01-01

Chirality is one of the ubiquitous phenomena in biological systems. The left handed (L-) amino acids and right handed (D-) sugars are normally found in proteins, and in RNAs and DNAs, respectively. The effect of chiral surfaces at the nanoscale on cellular uptake has, however, not been explored. This study reveals for the first time the molecular chirality on gold nanoparticles (AuNPs) functions as a direct regulator for cellular uptake. Monolayers of 2-mercaptoacetyl-L(D)-valine (L(D)-MAV) and poly(acryloyl-L(D)-valine (L(D)-PAV) chiral molecules were formed on AuNPs surface, respectively. The internalized amount of PAV-AuNPs was several times larger than that of MAV-AuNPs by A549 and HepG2 cells, regardless of the chirality difference. However, the D-PAV-AuNPs were internalized with significantly larger amount than the L-PAV-AuNPs. This chirality-dependent uptake effect is likely attributed to the preferable interaction between the L-phospholipid-based cell membrane and the D-enantiomers. PMID:27531648

Surface-anchored poly(acryloyl-L(D)-valine) with enhanced chirality-selective effect on cellular uptake of gold nanoparticles

NASA Astrophysics Data System (ADS)

Deng, Jun; Wu, Sai; Yao, Mengyun; Gao, Changyou

2016-08-01

Chirality is one of the ubiquitous phenomena in biological systems. The left handed (L-) amino acids and right handed (D-) sugars are normally found in proteins, and in RNAs and DNAs, respectively. The effect of chiral surfaces at the nanoscale on cellular uptake has, however, not been explored. This study reveals for the first time the molecular chirality on gold nanoparticles (AuNPs) functions as a direct regulator for cellular uptake. Monolayers of 2-mercaptoacetyl-L(D)-valine (L(D)-MAV) and poly(acryloyl-L(D)-valine (L(D)-PAV) chiral molecules were formed on AuNPs surface, respectively. The internalized amount of PAV-AuNPs was several times larger than that of MAV-AuNPs by A549 and HepG2 cells, regardless of the chirality difference. However, the D-PAV-AuNPs were internalized with significantly larger amount than the L-PAV-AuNPs. This chirality-dependent uptake effect is likely attributed to the preferable interaction between the L-phospholipid-based cell membrane and the D-enantiomers.

Surface-anchored poly(acryloyl-L(D)-valine) with enhanced chirality-selective effect on cellular uptake of gold nanoparticles.

PubMed

Deng, Jun; Wu, Sai; Yao, Mengyun; Gao, Changyou

2016-08-17

Chirality is one of the ubiquitous phenomena in biological systems. The left handed (L-) amino acids and right handed (D-) sugars are normally found in proteins, and in RNAs and DNAs, respectively. The effect of chiral surfaces at the nanoscale on cellular uptake has, however, not been explored. This study reveals for the first time the molecular chirality on gold nanoparticles (AuNPs) functions as a direct regulator for cellular uptake. Monolayers of 2-mercaptoacetyl-L(D)-valine (L(D)-MAV) and poly(acryloyl-L(D)-valine (L(D)-PAV) chiral molecules were formed on AuNPs surface, respectively. The internalized amount of PAV-AuNPs was several times larger than that of MAV-AuNPs by A549 and HepG2 cells, regardless of the chirality difference. However, the D-PAV-AuNPs were internalized with significantly larger amount than the L-PAV-AuNPs. This chirality-dependent uptake effect is likely attributed to the preferable interaction between the L-phospholipid-based cell membrane and the D-enantiomers.

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 ...

A resolution approach of racemic phenylalanine with aqueous two-phase systems of chiral tropine ionic liquids.

PubMed

Wu, Haoran; Yao, Shun; Qian, Guofei; Yao, Tian; Song, Hang

2015-10-30

Aqueous two-phase systems (ATPS) based on tropine type chiral ionic liquids and inorganic salt solution were designed and prepared for the enantiomeric separation of racemic phenylalanine. The phase behavior of IL-based ATPS was comprehensive investigated, and phase equilibrium data were correlated by Merchuk equation. Various factors were also systematically investigated for their influence on separation efficiency. Under the appropriate conditions (0.13g/g [C8Tropine]pro, 35mg/g Cu(Ac)2, 20mg/g d,l-phenylalanine, 0.51g/g H2O and 0.30g/g K2HPO4), the enantiomeric excess value of phenylalanine in solid phase (mainly containing l-enantiomer) was 65%. Finally, the interaction mechanism was studied via 1D and 2D NMR. The results indicate that d-enantiomer of phenylalanine interacts more strongly with chiral ILs and Cu(2+) based on the chiral ion-pairs space coordination mechanism, which makes it tend to remain in the top IL-rich phase. By contrast, l-enantiomer is transferred into the solid phase. Above chiral ionic liquids aqueous two-phase systems have demonstrated obvious resolution to racemic phenylalanine and could be promising alterative resolution approach for racemic amino acids in aqueous circumstance. Copyright © 2015. Published by Elsevier B.V.

Color superconductivity from the chiral quark-meson model

NASA Astrophysics Data System (ADS)

Sedrakian, Armen; Tripolt, Ralf-Arno; Wambach, Jochen

2018-05-01

We study the two-flavor color superconductivity of low-temperature quark matter in the vicinity of chiral phase transition in the quark-meson model where the interactions between quarks are generated by pion and sigma exchanges. Starting from the Nambu-Gorkov propagator in real-time formulation we obtain finite temperature (real axis) Eliashberg-type equations for the quark self-energies (gap functions) in terms of the in-medium spectral function of mesons. Exact numerical solutions of the coupled nonlinear integral equations for the real and imaginary parts of the gap function are obtained in the zero temperature limit using a model input spectral function. We find that these components of the gap display a complicated structure with the real part being strongly suppressed above 2Δ0, where Δ0 is its on-shell value. We find Δ0 ≃ 40MeV close to the chiral phase transition.

Chemical synthesis of water-soluble, chiral conducting-polymer complexes

DOEpatents

Wang, Hsing-Lin; McCarthy, Patrick A.; Yang, Sze Cheng

2003-01-01

The template-guided synthesis of water-soluble, chiral conducting polymer complexes is described. Synthesis of water-soluble polyaniline complexes is achieved by carefully controlling the experimental parameters such as; acid concentration, ionic strength, monomer/template ratio, total reagent concentration, and order of reagent addition. Chiral (helical) polyaniline complexes can be synthesized by addition of a chiral inducing agent (chiral acid) prior to polymerization, and the polyaniline helix can be controlled by the addition of the (+) or (-) form of the chiral acid. Moreover the quantity of chiral acid and the salt content has a significant impact on the degree of chirality in the final polymer complexes. The polyaniline and the template have been found to be mixed at the molecular level which results in chiral complexes that are robust through repeated doping and dedoping cycles.

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

PubMed

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

2017-01-24

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

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

Chiral metamirrors for broadband spin-selective absorption

NASA Astrophysics Data System (ADS)

Jing, Liqiao; Wang, Zuojia; Yang, Yihao; Zheng, Bin; Liu, Yongmin; Chen, Hongsheng

2017-06-01

Chiral metamirrors are recently proposed metadevices that have the ability of selective reflection for the designated circularly polarized waves. However, previous chiral metamirrors only work in a narrow band, which would limit their potential applications in engineering. Here, we propose an approach towards broadband spin-selective absorption. By combining the chiral resonant modes of two asymmetric split-ring resonators, we design and construct a chiral metamirror that absorbs only the left-handed circularly waves over a broad frequency range. The measured results show a bandwidth of 5.1%, almost 96% larger than that of the narrowband metamirror. Furthermore, the proposed chiral metamirror exhibits prominent performance at oblique incidence, even when high-order diffraction appears. The total thickness of the metamirror is only one-ninth of the wavelength, highly suitable for on-chip integration. Our findings may provide an efficient approach to boost the working bandwidth of the chiral metamirror and could advance its applications in optical instruments.

Validated chiral high performance liquid chromatography separation method and simulation studies of dipeptides on amylose chiral column.

PubMed

Ali, Imran; Sahoo, Dibya Ranjan; ALOthman, Zeid A; Alwarthan, Abdulrahman A; Asnin, Leonid; Larsson, Bernt

2015-08-07

Chiral resolution of dl-alanine-dl-tyrosine and dl-leucine-dl-phenylalanine dipeptides was achieved on AmyCoat-RP column. The mobile phase used for dl-alanine-dl-tyrosine was acetonitrile-ammonium acetate (10mM, pH 6.0) [50:50, v/v]. It was acetonitrile-methanol-ammonium acetate (10mM; pH adjusted to 4.5 with glacial acetic acid) [50:20:30, v/v] for dl-leucine-dl-phenylalanine. The flow rate of the mobile phases was 0.8mL/min with UV detection at 275nm. The values of retention factors for ll-, dd-, dl- and ld-stereomers of dl-alanine-dl-tyrosine were 1.71, 2.86, 5.43 and 9.42, respectively. The values of separation and resolution factors were 1.67, 1.90 and 1.73 and 2.88, 6.43 and 7.90, respectively. Similarly, these values for dl-leucine-dl-phenylalanine stereomers were 1.50, 2.88, 3.50 and 4.07 (retention factors), 1.92, 1.22 and 1.62 (separation factors) and 2.67, 1.55 and 2.30 (resolution factors). The limits of detections and quantitation were ranged from 2.03 to 6.40 and 6.79 to 21.30μg/mL, respectively. The modeling studies were in agreement with the elution orders. The mechanism of chiral recognition was established by modeling and chromatographic studies. It was observed that hydrogen bondings and π-π interactions are the major forces for chiral separation. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

Lectures on Chiral Symmetries and Soft Pion Processes

DOE R&D Accomplishments Database

Nambu, Y.

1966-08-01

At the Istanbul Summer School in 1962 I gave lectures on "Chiral Symmetries in Weak and Strong Interactions." It is only recently, however, that the basic ideas that were started several years ago have begun to bear fruit. We will cover in the present lectures more or less the same general field, but certainly there will be a lot more results to be discussed now than four years ago.

Spin-flavor structure of chiral-odd generalized parton distributions in the large- N c limit

DOE PAGES

Schweitzer, P.; Weiss, C.

2016-10-05

We study the spin-flavor structure of the nucleon's chiral-odd generalized parton distributions (transversity GPDs) in the large-N c limit of QCD. In contrast to the chiral-even case, only three combinations of the four chiral-odd GPDs are nonzero in the leading order of the 1/N c expansion: E-bar T = E T+2H-tilde T, H T, and E-tilde T. The degeneracy is explained by the absence of spin-orbit interactions correlating the transverse momentum transfer with the transverse quark spin. It can also be deduced from the natural N c scaling of the quark-nucleon helicity amplitudes associated with the GPDs. In the GPDmore » E-bar T the flavor-singlet component u+d is leading in the 1/N c expansion, while in H T and E-tilde T it is the flavor-nonsinglet components u–d. Furthermore, the large-N c relations are consistent with the spin-flavor structure extracted from hard exclusive π 0 and η electroproduction data, if it is assumed that the processes are mediated by twist-3 amplitudes involving the chiral-odd GPDs and the chiral-odd pseudoscalar meson distribution amplitudes.« less

Scale-setting, flavor dependence, and chiral symmetry restoration

DOE PAGES

Binosi, D; Roberts, Craig D.; Rodriguez-Quintero, J.

2017-06-13

Here, we determine the flavor dependence of the renormalization-group-invariant running interaction through judicious use of both unquenched Dyson-Schwinger equation and lattice results for QCD’s gauge-sector two-point functions. An important step is the introduction of a physical scale setting procedure that enables a realistic expression of the effect of different numbers of active quark flavours on the interaction. Using this running interaction in concert with a well constrained class of dressed–gluon-quark vertices, we estimate the critical number of active lighter-quarks above which dynamical chiral symmetry breaking becomes impossible: n cr f ≈ 9; and hence in whose neighborhood QCD is plausiblymore » a conformal theory.« less

Chiral dynamics with (non)strange quarks

NASA Astrophysics Data System (ADS)

Kubis, Bastian; Meißner, Ulf-G.

2017-01-01

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

Chirality-induced negative refraction in magnetized plasma

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 themore » external magnetic field can result in greater range negative refraction. Parameter dependence of the effects is calculated and discussed.« less

A web site for calculating the degree of chirality.

PubMed

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

2011-01-01

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

Staggered heavy baryon chiral perturbation theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

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}}{supmore » 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.« less

Chiral transcription in self-assembled tetrahedral Eu 4L 6 chiral cages displaying sizable circularly polarized luminescence

DOE PAGES

Yeung, Chi -Tung; Yim, King -Him; Wong, Ho -Yin; ...

2017-10-24

Predictable stereoselective formation of supramolecular assembly is generally believed to be an important but complicated process. Here, we show that point chirality of a ligand decisively influences its supramolecular assembly behavior. We designed three closely related chiral ligands with different point chiralities, and observe their self-assembly into europium (Eu) tetrametallic tetrahedral cages. One ligand exhibits a highly diastereoselective assembly into homochiral (either ΔΔΔΔ or ΛΛΛΛ) Eu tetrahedral cages whereas the two other ligands, with two different approaches of loosened point chirality, lead to a significant breakdown of the diastereoselectivity to generate a mixture of (ΔΔΔΔ and ΛΛΛΛ) isomers. The cagesmore » are highly emissive (luminescence quantum yields of 16(1) to 18(1)%) and exhibit impressive circularly polarized luminescence properties (|g lum |: up to 0.16). With in-depth studies, we present an example that correlates the nonlinear enhancement of the chiroptical response to the nonlinearity dependence on point chirality.« less

The topological susceptibility from grand canonical simulations in the interacting instanton liquid model: Chiral phase transition and axion mass

NASA Astrophysics Data System (ADS)

Wantz, Olivier; Shellard, E. P. S.

2010-04-01

This is the last in a series of papers on the topological susceptibility in the interacting instanton liquid model (IILM). We will derive improved finite temperature interactions to study the thermodynamic limit of grand canonical Monte Carlo simulations in the quenched and unquenched case with light, physical quark masses. In particular, we will be interested in chiral symmetry breaking. The paper culminates by giving, for the first time, a well-motivated temperature-dependent axion mass. Especially, this work finally provides a computation of the axion mass in the low temperature regime, ma2fa2=1.46×10-3Λ41+0.50 T/Λ1+(3.53 . It connects smoothly to the high temperature dilute gas approximation; the latter is improved by including quark threshold effects. To compare with earlier studies, we also provide the usual power-law ma2=αΛ4fa2(T, where Λ=400 MeV, n=6.68 and α=1.68×10-7.

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.

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.

Chiral magnetic effect in condensed matter systems

NASA Astrophysics Data System (ADS)

Li, Qiang; Kharzeev, Dmitri E.

2016-12-01

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