361 research outputs found
Chiral Crystal Growth under Grinding
To study the establishment of homochirality observed in the crystal growth
experiment of chiral molecules from a solution under grinding, we extend the
lattice gas model of crystal growth as follows. A lattice site can be occupied
by a chiral molecule in R or S form, or can be empty. Molecules form
homoclusters by nearest neighbor bonds. They change their chirality if they are
isolated monomers in the solution. Grinding is incorporated by cutting and
shafling the system randomly. It is shown that Ostwald ripening without
grinding is extremely slow to select chirality, if possible. Grinding alone
also cannot achieve chirality selection. For the accomplishment of
homochirality, we need an enhanced chirality change on crystalline surface.
With this "autocatalytic effect" and the recycling of monomers due to rinding,
an exponential increase of crystal enantiomeric excess to homochiral state is
realized.Comment: 10 pages, 5 figure
Chirality transfer and stereo-selectivity of imprinted cholesteric networks
Imprinting of cholesteric textures in a polymer network is a method of
preserving a macroscopically chiral phase in a system with no molecular
chirality. By modifying the elastics properties of the network, the resulting
stored helical twist can be manipulated within a wide range since the
imprinting efficiency depends on the balance between the elastics constants and
twisting power at network formation. One spectacular property of phase
chirality imprinting is the created ability of the network to adsorb
preferentially one stereo-component from a racemic mixture. In this paper we
explore this property of chirality transfer from a macroscopic to the molecular
scale. In particular, we focus on the competition between the phase chirality
and the local nematic order. We demonstrate that it is possible to control the
subsequent release of chiral solvent component from the imprinting network and
the reversibility of the stereo-selective swelling by racemic solvents
Stochastic Approach to Enantiomeric Excess Amplification and Chiral Symmetry Breaking
Stochastic aspects of chemical reaction models related to the Soai reactions
as well as to the homochirality in life are studied analytically and
numerically by the use of the master equation and random walk model. For
systems with a recycling process, a unique final probability distribution is
obtained by means of detailed balance conditions. With a nonlinear
autocatalysis the distribution has a double-peak structure, indicating the
chiral symmetry breaking. This problem is further analyzed by examining
eigenvalues and eigenfunctions of the master equation. In the case without
recycling process, final probability distributions depend on the initial
conditions. In the nonlinear autocatalytic case, time-evolution starting from a
complete achiral state leads to a final distribution which differs from that
deduced from the nonzero recycling result. This is due to the absence of the
detailed balance, and a directed random walk model is shown to give the correct
final profile. When the nonlinear autocatalysis is sufficiently strong and the
initial state is achiral, the final probability distribution has a double-peak
structure, related to the enantiomeric excess amplification. It is argued that
with autocatalyses and a very small but nonzero spontaneous production, a
single mother scenario could be a main mechanism to produce the homochirality.Comment: 25 pages, 6 figure
DNA barcode assessment and population structure of aphidophagous hoverfly <i>Sphaerophoria scripta</i>:Implications for conservation biological control
With the advent of integrated pest management, the conservation of indigenous populations of natural enemies of pest species has become a relevant practice, necessitating the accurate identification of beneficial species and the inspection of evolutionary mechanisms affecting the long-time persistence of their populations. The long hoverfly,Sphaerophoria scripta, represents one of the most potent aphidophagous control agents due to a worldwide distribution and a favorable constellation of biological traits. Therefore, we assessed five EuropeanS. scriptapopulations by combining molecular (cytochromecoxidase subunit I-COI, internal transcribed spacer 2-ITS2, and allozyme loci) and morphological (wing size and shape) characters.COIsequences retrieved in this study were conjointly analyzed with BOLD/GenBank sequences of the otherSphaerophoriaspecies to evaluate whetherCOIpossessed a sufficient diagnostic value as a DNA barcode marker to consistently delimit allospecific individuals. Additionally, the aforementioned characters were used to inspect the population structure ofS. scriptain Europe using methods based on individual- and population-based genetic differences, as well as geometric morphometrics of wing traits. The results indicate numerous sharedCOIhaplotypes among differentSphaerophoriaspecies, thus disqualifying this marker from being an adequate barcoding region in this genus. Conversely, the analyses of population structuring revealed high population connectivity across Europe, therefore indicating strong tolerance ofS. scriptato environmental heterogeneity. The results imply a multilocus approach as the next step in molecular identification of differentSphaerophoriaspecies, while confirming the status ofS. scriptaas a powerful biocontrol agent of economically relevant aphid pests
Order and Frustration in Chiral Liquid Crystals
This paper reviews the complex ordered structures induced by chirality in
liquid crystals. In general, chirality favors a twist in the orientation of
liquid-crystal molecules. In some cases, as in the cholesteric phase, this
favored twist can be achieved without any defects. More often, the favored
twist competes with applied electric or magnetic fields or with geometric
constraints, leading to frustration. In response to this frustration, the
system develops ordered structures with periodic arrays of defects. The
simplest example of such a structure is the lattice of domains and domain walls
in a cholesteric phase under a magnetic field. More complex examples include
defect structures formed in two-dimensional films of chiral liquid crystals.
The same considerations of chirality and defects apply to three-dimensional
structures, such as the twist-grain-boundary and moire phases.Comment: 39 pages, RevTeX, 14 included eps figure
From Monasteries to Multinationals (and Back): A Historical Review of the Beer Economy
Genetic variability in three species of Gymnotus Linnaeus, 1758 (Gymnotiformes: Gymnotidae) from Caracu stream of the upper Paraná River basin, Brazil
Fluctuation Induced Homochirality
We propose a new mechanism for the achievment of homochirality in life
without any autocatalytic production process. Our model consists of a
spontaneous production together with a recycling cross inhibition in a closed
system.
It is shown that although the rate equations for this system predict no
chiral symmetry breaking, the stochastic master equation predicts complete
homochirality. This is because the fluctuation induced by the discreteness of
population numbers of participating molecules plays essential roles. This
fluctuation conspires with the recyling cross inhibition to realize the
homochirality.Comment: 13 pages, 6 figure
Quantum formulation for nanoscale optical and material chirality: symmetry issues, space and time parity, and observables
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 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
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