9,471 research outputs found
Topological characterization of crystalline ice structures from coordination sequences
Topological properties of crystalline ice structures are studied by
considering ring statistics, coordination sequences, and topological density of
different ice phases. The coordination sequences (number of sites at
topological distance k from a reference site) have been obtained by direct
enumeration until at least 40 coordination spheres for different ice
polymorphs. This allows us to study the asymptotic behavior of the mean number
of sites in the k-th shell, M_k, for high values of k: M_k ~ a k^2, a being a
structure-dependent parameter. Small departures from a strict parabolic
dependence have been studied by considering first and second differences of the
series {M_k} for each structure. The parameter a ranges from 2.00 for ice VI to
4.27 for ice XII, and is used to define a topological density for these solid
phases of water. Correlations between such topological density and the actual
volume of ice phases are discussed. Ices Ih and Ic are found to depart from the
general trend in this correlation due to the large void space in their
structures.Comment: 10 pages, 7 figures, 3 table
Molecular Tilt on Monolayer-Protected Nanoparticles
The structure of the tilted phase of monolayer-protected nanoparticles is investigated by means of a simple Ginzburg-Landau model. The theory contains two dimensionless parameters representing the preferential tilt angle and the ratio (epsilon) between the energy cost due to spatial variations in the tilt of the coating molecules and that of the van der Waals interactions which favors uniform tilt. We analyze the model for both spherical and octahedral particles. On spherical particles, we find a transition from a tilted phase, at small (epsilon), to a phase where the molecules spontaneously align along the surface normal and tilt disappears. Octahedral particles have an additional phase at small characterized by the presence of six topological defects. These defective configurations provide preferred sites for the chemical functionalization of monolayer-protected nanoparticles via place-exchange reactions and their consequent linking to form molecules and\ud
bulk materials
Analysis of Three-Dimensional Protein Images
A fundamental goal of research in molecular biology is to understand protein
structure. Protein crystallography is currently the most successful method for
determining the three-dimensional (3D) conformation of a protein, yet it
remains labor intensive and relies on an expert's ability to derive and
evaluate a protein scene model. In this paper, the problem of protein structure
determination is formulated as an exercise in scene analysis. A computational
methodology is presented in which a 3D image of a protein is segmented into a
graph of critical points. Bayesian and certainty factor approaches are
described and used to analyze critical point graphs and identify meaningful
substructures, such as alpha-helices and beta-sheets. Results of applying the
methodologies to protein images at low and medium resolution are reported. The
research is related to approaches to representation, segmentation and
classification in vision, as well as to top-down approaches to protein
structure prediction.Comment: See http://www.jair.org/ for any accompanying file
Helical Chirality: a Link between Local Interactions and Global Topology in DNA
DNA supercoiling plays a major role in many cellular functions. The global DNA conformation is however intimately linked to local DNA-DNA interactions influencing both the physical properties and the biological functions of the supercoiled molecule. Juxtaposition of DNA double helices in ubiquitous crossover arrangements participates in multiple functions such as recombination, gene regulation and DNA packaging. However, little is currently known about how the structure and stability of direct DNA-DNA interactions influence the topological state of DNA. Here, a crystallographic analysis shows that due to the intrinsic helical chirality of DNA, crossovers of opposite handedness exhibit markedly different geometries. While right-handed crossovers are self-fitted by sequence-specific groove-backbone interaction and bridging Mg2+ sites, left-handed crossovers are juxtaposed by groove-groove interaction. Our previous calculations have shown that the different geometries result in differential stabilisation in solution, in the presence of divalent cations. The present study reveals that the various topological states of the cell are associated with different inter-segmental interactions. While the unstable left-handed crossovers are exclusively formed in negatively supercoiled DNA, stable right-handed crossovers constitute the local signature of an unusual topological state in the cell, such as the positively supercoiled or relaxed DNA. These findings not only provide a simple mechanism for locally sensing the DNA topology but also lead to the prediction that, due to their different tertiary intra-molecular interactions, supercoiled molecules of opposite signs must display markedly different physical properties. Sticky inter-segmental interactions in positively supercoiled or relaxed DNA are expected to greatly slow down the slithering dynamics of DNA. We therefore suggest that the intrinsic helical chirality of DNA may have oriented the early evolutionary choices for DNA topology
Design of crystal-like aperiodic solids with selective disorder--phonon coupling
Functional materials design normally focuses on structurally-ordered systems
because disorder is considered detrimental to many important physical
properties. Here we challenge this paradigm by showing that particular types of
strongly-correlated disorder can give rise to useful characteristics that are
inaccessible to ordered states. A judicious combination of low-symmetry
building unit and high-symmetry topological template leads to aperiodic
"procrystalline" solids that harbour this type of topological disorder. We
identify key classes of procrystalline states together with their
characteristic diffraction behaviour, and establish a variety of mappings onto
known and target materials. Crucially, the strongly-correlated disorder we
consider is associated with specific sets of modulation periodicities
distributed throughout the Brillouin zone. Lattice dynamical calculations
reveal selective disorder-phonon coupling to lattice vibrations characterised
by these same periodicities. The principal effect on the phonon spectrum is to
bring about dispersion in energy rather than wave-vector, as in the
poorly-understood "waterfall" effect observed in relaxor ferroelectrics. This
property of procrystalline solids suggests a mechanism by which
strongly-correlated topological disorder might allow new and useful
functionalities, including independently-optimised thermal and electronic
transport behaviour as required for high-performance thermoelectrics.Comment: 4 figure
Unprecedented chemical transformation: crystallographic evidence for 1,1,2,2-tetrahydroxyethane captured within an Fe6Dy3 single molecule magnet
A nonanuclear {Fe6Dy3} coordination cluster displaying SMM
behaviour in which an unprecedented chemical transformation
provides structural information for the existence of 1,1,2,2-tetrahydroxyethane
is reported
Long range coherent magnetic bound states in superconductors
The quantum coherent coupling of completely different degrees of freedom is a
challenging path towards creating new functionalities for quantum electronics.
Usually the antagonistic coupling between spins of magnetic impurities and
superconductivity leads to the destruction of the superconducting order. Here
we show that a localized classical spin of an iron atom immersed in a
superconducting condensate can give rise to new kind of long range coherent
magnetic quantum state. In addition to the well-known Shiba bound state present
on top of an impurity we reveal the existence of a star shaped pattern which
extends as far as 12 nm from the impurity location. This large spatial
dispersion turns out to be related, in a non-trivial way, to the
superconducting coherence length. Inside star branches we observed short scale
interference fringes with a particle-hole asymmetry. Our theoretical approach
captures these features and relates them to the electronic band structure and
the Fermi wave length of the superconductor. The discovery of a directional
long range effect implies that distant magnetic atoms could coherently interact
leading to new topological superconducting phases with fascinating properties
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