1,183 research outputs found
On the Stereochemistry of the Cations in the Doping Block of Superconducting Copper-Oxides
Metal-oxygen complexes containing Cu,- Tl-, Hg-, Bi- and Pb-cations are
electronically active in superconducting copper-oxides by stabilizing single
phases with enhanced , whereas other metal-oxygen complexes deteriorate
copper-oxide superconductivity. Cu, Tl, Hg, Bi, Pb in their actual oxidation
states are closed shell or inert pair ions. Their electronic
configurations have a strong tendency to polarize the oxygen environment. The
closed shell ions with low lying
excitations form linear complexes through hybridization polarizing
the apical oxygens. Comparatively low excitation energies
distinguish from other closed shell
ions deteriorating copper-oxide superconductivity, {\it e.g.} .Comment: 5 pages, uses REVTEX. To be published in: J. Superconductivity, Proc.
Int. Workshop on "Phase Separation, Electronic Inhomogenities and Related
Mechanisms for High T_c Superconductors", Erice (Sicily) 9-15 July 199
The origin of large molecules in primordial autocatalytic reaction networks
Large molecules such as proteins and nucleic acids are crucial for life, yet
their primordial origin remains a major puzzle. The production of large
molecules, as we know it today, requires good catalysts, and the only good
catalysts we know that can accomplish this task consist of large molecules.
Thus the origin of large molecules is a chicken and egg problem in chemistry.
Here we present a mechanism, based on autocatalytic sets (ACSs), that is a
possible solution to this problem. We discuss a mathematical model describing
the population dynamics of molecules in a stylized but prebiotically plausible
chemistry. Large molecules can be produced in this chemistry by the coalescing
of smaller ones, with the smallest molecules, the `food set', being buffered.
Some of the reactions can be catalyzed by molecules within the chemistry with
varying catalytic strengths. Normally the concentrations of large molecules in
such a scenario are very small, diminishing exponentially with their size.
ACSs, if present in the catalytic network, can focus the resources of the
system into a sparse set of molecules. ACSs can produce a bistability in the
population dynamics and, in particular, steady states wherein the ACS molecules
dominate the population. However to reach these steady states from initial
conditions that contain only the food set typically requires very large
catalytic strengths, growing exponentially with the size of the catalyst
molecule. We present a solution to this problem by studying `nested ACSs', a
structure in which a small ACS is connected to a larger one and reinforces it.
We show that when the network contains a cascade of nested ACSs with the
catalytic strengths of molecules increasing gradually with their size (e.g., as
a power law), a sparse subset of molecules including some very large molecules
can come to dominate the system.Comment: 49 pages, 17 figures including supporting informatio
Non-Enzymatic Decomposition of Collagen Fibers by a Biglycan Antibody and a Plausible Mechanism for Rheumatoid Arthritis
Rheumatoid arthritis (RA) is a systemic autoimmune inflammatory and destructive joint disorder that affects tens of millions of people worldwide. Normal healthy joints maintain a balance between the synthesis of extracellular matrix (ECM) molecules and the proteolytic degradation of damaged ones. In the case of RA, this balance is shifted toward matrix destruction due to increased production of cleavage enzymes and the presence of (autoimmune) immunoglobulins resulting from an inflammation induced immune response. Herein we demonstrate that a polyclonal antibody against the proteoglycan biglycan (BG) causes tissue destruction that may be analogous to that of RA affected tissues. The effect of the antibody is more potent than harsh chemical and/or enzymatic treatments designed to mimic arthritis-like fibril de-polymerization. In RA cases, the immune response to inflammation causes synovial fibroblasts, monocytes and macrophages to produce cytokines and secrete matrix remodeling enzymes, whereas B cells are stimulated to produce immunoglobulins. The specific antigen that causes the RA immune response has not yet been identified, although possible candidates have been proposed, including collagen types I and II, and proteoglycans (PG's) such as biglycan. We speculate that the initiation of RA associated tissue destruction in vivo may involve a similar non-enzymatic decomposition of collagen fibrils via the immunoglobulins themselves that we observe here ex vivo
Chiral and herringbone symmetry breaking in water-surface monolayers
We report the observation from monolayers of eicosanoic acid in the L′2 phase of three distinct out-of-plane first-order diffraction peaks, indicating molecular tilt in a nonsymmetry direction and hence the absence of mirror symmetry. At lower pressures the molecules tilt in the direction of their nearest neighbors. In this region we find a structural transition, which we tentatively identify as the rotator-herringbone transition L2d−L2h
Gridmapping the northern plains of Mars: Geomorphological, Radar and Water-Equivalent Hydrogen results from Arcadia Plantia
A project of mapping ice-related landforms was undertaken to understand the role of sub-surface ice in the northern plains. This work is the first continuous regional mapping from CTX (“ConTeXt Camera”, 6 m/pixel; Malin et al., 2007) imagery in Arcadia Planitia along a strip 300 km across stretching from 30°N to 80°N centred on the 170° West line of longitude. The distribution and morphotypes of these landforms were used to understand the permafrost cryolithology. The mantled and textured signatures occur almost ubiquitously between 35° N and 78° N and have a positive spatial correlation with inferred ice stability based on thermal modelling, neutron spectroscopy and radar data. The degradational features into the LDM (Latitude Dependent Mantle) include pits, scallops and 100 m polygons and provide supporting evidence for sub-surface ice and volatile loss between 35-70° N in Arcadia with the mantle between 70-78° N appearing much more intact. Pitted terrain appears to be much more pervasive in Arcadia than in Acidalia and Utopia suggesting that the Arcadia study area had more wide-spread near-surface sub-surface ice, and thus was more susceptible to pitting, or that the ice was less well-buried by sediments. Correlations with ice stability models suggest that lack of pits north of 65-70° N could indicate a relatively young age (~1Ma), however this could also be explained through regional variations in degradation rates. The deposition of the LDM is consistent with an airfall hypothesis however there appears to be substantial evidence for fluvial processes in southern Arcadia with older, underlying processes being equally dominant with the LDM and degradation thereof in shaping the landscape
Dissociation in a polymerization model of homochirality
A fully self-contained model of homochirality is presented that contains the
effects of both polymerization and dissociation. The dissociation fragments are
assumed to replenish the substrate from which new monomers can grow and undergo
new polymerization. The mean length of isotactic polymers is found to grow
slowly with the normalized total number of corresponding building blocks.
Alternatively, if one assumes that the dissociation fragments themselves can
polymerize further, then this corresponds to a strong source of short polymers,
and an unrealistically short average length of only 3. By contrast, without
dissociation, isotactic polymers becomes infinitely long.Comment: 16 pages, 6 figures, submitted to Orig. Life Evol. Biosp
Origin of magnetoelectric behavior in BiFeO
The magnetoelectric behavior of BiFeO has been explored on the basis of
accurate density functional calculations. The structural, electronic, magnetic,
and ferroelectric properties of BiFeO are predicted correctly without
including strong correlation effect in the calculation. Moreover, the
experimentally-observed elongation of cubic perovskite-like lattice along the
[111] direction is correctly reproduced. At high pressure we predicted a
pressure-induced structural transition and the total energy calculations at
expanded lattice show two lower energy ferroelectric phases, closer in energy
to the ground state phase. Band-structure calculations show that BiFeO will
be an insulator in A- and G-type antiferromagnetic phases and a metal in other
magnetic configurations. Chemical bonding in BiFeO has been analyzed using
various tools and electron localization function analysis shows that
stereochemically active lone-pair electrons at the Bi sites are responsible for
displacements of the Bi atoms from the centro-symmetric to the
noncentrosymmetric structure and hence the ferroelectricity. A large
ferroelectric polarization (88.7 C/cm) is predicted in accordance
with recent experimental findings. The net polarization is found to mainly (
98%) originate from Bi atoms. Moreover the large scatter in experimentally
reported polarization values is due to the large anisotropy in the spontaneous
polarization.Comment: 19 pages, 12 figures, 4 table
Chiral Polymerization in Open Systems From Chiral-Selective Reaction Rates
We investigate the possibility that prebiotic homochirality can be achieved
exclusively through chiral-selective reaction rate parameters without any other
explicit mechanism for chiral bias. Specifically, we examine an open network of
polymerization reactions, where the reaction rates can have chiral-selective
values. The reactions are neither autocatalytic nor do they contain explicit
enantiomeric cross-inhibition terms. We are thus investigating how rare a set
of chiral-selective reaction rates needs to be in order to generate a
reasonable amount of chiral bias. We quantify our results adopting a
statistical approach: varying both the mean value and the rms dispersion of the
relevant reaction rates, we show that moderate to high levels of chiral excess
can be achieved with fairly small chiral bias, below 10%. Considering the
various unknowns related to prebiotic chemical networks in early Earth and the
dependence of reaction rates to environmental properties such as temperature
and pressure variations, we argue that homochirality could have been achieved
from moderate amounts of chiral selectivity in the reaction rates.Comment: 15 pages, 6 figures, accepted for publication in Origins of Life and
Evolution of Biosphere
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The biomechanics of amnion rupture: an X-ray diffraction study
Pre-term birth is the leading cause of perinatal and neonatal mortality, 40% of which are attributed to the pre-term premature rupture of amnion. Rupture of amnion is thought to be associated with a corresponding decrease in the extracellular collagen content and/or increase in collagenase activity. However, there is very little information concerning the detailed organisation of fibrillar collagen in amnion and how this might influence rupture. Here we identify a loss of lattice like arrangement in collagen organisation from areas near to the rupture site, and present a 9% increase in fibril spacing and a 50% decrease in fibrillar organisation using quantitative measurements gained by transmission electron microscopy and the novel application of synchrotron X-ray diffraction. These data provide an accurate insight into the biomechanical process of amnion rupture and highlight X-ray diffraction as a new and powerful tool in our understanding of this process
The origin of life: chemical evolution of a metabolic system in a mineral honeycomb?
For the RNA-world hypothesis to be ecologically feasible, selection mechanisms acting on replicator communities need to be invoked and the corresponding scenarios of molecular evolution specified. Complementing our previous models of chemical evolution on mineral surfaces, in which selection was the consequence of the limited mobility of macromolecules attached to the surface, here we offer an alternative realization of prebiotic group-level selection: the physical encapsulation of local replicator communities into the pores of the mineral substrate. Based on cellular automaton simulations we argue that the effect of group selection in a mineral honeycomb could have been efficient enough to keep prebiotic ribozymes of different specificities and replication rates coexistent, and their metabolic cooperation protected from extensive molecular parasitism. We suggest that mutants of the mild parasites persistent in the metabolic system can acquire useful functions such as replicase activity or the production of membrane components, thus opening the way for the evolution of the first autonomous protocells on Earth
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