Optimized Structures and Proton Affinities of Fluorinated Dimethyl Ethers: An Ab Initio Study

Ab initio methods have been used to investigate the proton affinity and the geometry changes upon protonation for the molecules (CH3)2O, (CH2F)2O, (CHF2)2O, and (CF3)2O. Geometry optimizations were performed at the MP2/3-2 I G level, and the resulting geometries were used for single-point energy MP2/6-31G calculations. The proton affinity calculated for (CH3)2O was 7 Kjoule/mole from the experimental value, within the desired variance of +/- 8Kjoule/mole for G2 theory, suggesting that the methodology used in this study is adequate for energy difference considerations. For (CF3)20, the calculated proton affinity of 602 Kjoule/mole suggests that perfluorinated ether molecules do not act as Lewis bases under normal circumstances; e.g. degradation of commercial lubricants in tribological applications

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 $T_c$, whereas other metal-oxygen complexes deteriorate copper-oxide superconductivity. Cu, Tl, Hg, Bi, Pb in their actual oxidation states are closed shell $d^{10}$ or inert $s^2$ pair ions. Their electronic configurations have a strong tendency to polarize the oxygen environment. The closed shell $d$ ions with low lying $nd^{10}\leftrightarrow nd^9(n+1)s$ excitations form linear complexes through $d_{z^2}-s$ hybridization polarizing the apical oxygens. Comparatively low $nd^9(n+1)s$ excitation energies distinguish $\rm Cu^{1+,3+}, Tl^{3+}, Hg^{2+}$ from other closed shell $d^{10}$ ions deteriorating copper-oxide superconductivity, {\it e.g.} $\rm Zn^{2+}$.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

One-Center Charge Transfer Transitions in Manganites

In frames of a rather conventional cluster approach, which combines the crystal field and the ligand field models we have considered different charge transfer (CT) states and O 2p-Mn 3d CT transitions in MnO$_{6}^{9-}$ octahedra. The many-electron dipole transition matrix elements were calculated using the Racah algebra for the cubic point group. Simple "local" approximation allowed to calculate the relative intensity for all dipole-allowed $\pi -\pi$ and $\sigma -\sigma$ CT transitions. We present a self-consistent description of the CT bands in insulating stoichiometric LaMn$^{3+}$O$_3$ compound with the only Mn$^{3+}$ valent state and idealized octahedral MnO$_{6}^{9-}$ centers which allows to substantially correct the current interpretation of the optical spectra. Our analysis shows the multi-band structure of the CT optical response with the weak low-energy edge at 1.7 eV, associated with forbidden $t_{1g}(\pi)-e_{g}$ transition and a series of the weak and strong dipole-allowed high-energy transitions starting from 2.5 and 4.5 eV, respectively, and extending up to nearly 11 eV. The most intensive features are associated with two strong composite bands near $4.6\div 4.7$ eV and $8\div 9$ eV, respectively, resulting from the superposition of the dipole-allowed $\sigma -\sigma$ and $\pi -\pi$ CT transitions. These predictions are in good agreement with experimental spectra. The experimental data point to a strong overscreening of the crystal field parameter $Dq$ in the CT states of MnO$_{6}^{9-}$ centers.Comment: 10 pages, 3 figure

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

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

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

Homochiral growth through enantiomeric cross-inhibition

The stability and conservation properties of a recently proposed polymerization model are studied. The achiral (racemic) solution is linearly unstable once the relevant control parameter (here the fidelity of the catalyst) exceeds a critical value. The growth rate is calculated for different fidelity parameters and cross-inhibition rates. A chirality parameter is defined and shown to be conserved by the nonlinear terms of the model. Finally, a truncated version of the model is used to derive a set of two ordinary differential equations and it is argued that these equations are more realistic than those used in earlier models of that form.Comment: 20 pages, 6 figures, Orig. Life Evol. Biosph. (accepted

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

Origin of Life

The evolution of life has been a big enigma despite rapid advancements in the fields of biochemistry, astrobiology, and astrophysics in recent years. The answer to this puzzle has been as mind-boggling as the riddle relating to evolution of Universe itself. Despite the fact that panspermia has gained considerable support as a viable explanation for origin of life on the Earth and elsewhere in the Universe, the issue remains far from a tangible solution. This paper examines the various prevailing hypotheses regarding origin of life like abiogenesis, RNA World, Iron-sulphur World, and panspermia; and concludes that delivery of life-bearing organic molecules by the comets in the early epoch of the Earth alone possibly was not responsible for kick-starting the process of evolution of life on our planet.Comment: 32 pages, 8 figures,invited review article, minor additio

Nanoscale structure of type I collagen fibrils: Quantitative measurement of D‐spacing

This article details a quantitative method to measure the D‐periodic spacing of type I collagen fibrils using atomic force microscopy coupled with analysis using a two‐dimensional fast fourier transform approach. Instrument calibration, data sampling and data analysis are discussed and comparisons of the data to the complementary methods of electron microscopy and X‐ray scattering are made. Examples of the application of this new approach to the analysis of type I collagen morphology in disease models of estrogen depletion and osteogenesis imperfecta (OI) are provided. We demonstrate that it is the D‐spacing distribution, not the D‐spacing mean, that showed statistically significant differences in estrogen depletion associated with early stage osteoporosis and OI. The ability to quantitatively characterize nanoscale morphological features of type I collagen fibrils will provide important structural information regarding type I collagen in many research areas, including tissue aging and disease, tissue engineering, and gene knockout studies. Furthermore, we also envision potential clinical applications including evaluation of tissue collagen integrity under the impact of diseases or drug treatments. The distribution of Type I collagen fibril D‐spacing provides important morphological information regarding Type I collagen in diseases such as early stages of osteoporosis and osteogenesis Imperfecta . In this article, the authors use Atomic Force Microscopy (AFM) imaging combined with two Dimensional Fast Fourier Transform (2D FFT) analysis to quantitatively assess Type I collagen fibril D‐spacing. This methodology allows imaging and characterization of Type I collagen constituted biological tissues, hydrogels, and other collagen based biomaterials.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/94732/1/117_ftp.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/94732/2/biot_201200174_sm_suppinfo.pd