Polymer precursors for ceramic matrix composites

The synthesis and characterization of a polycyclohexasilane is reported. Because of its cyclic structure, it is anticipated that this polymer might serve as a precursor to SIC having a high char yield with little rearrangement to form small, volatile cyclic silanes, and, as such, would be of interest as a precursor to SiC composite matrices and fibers, or as a binder in ceramic processing. Several approaches to the synthesis of a bifunctional cyclic monomer were attempted; the most successful of these was metal coupling of PhMeSiCl2 and Me2SiCl2. The procedure gives six-membered ring compounds with all degrees of phenyl substitution, from none to hexaphenyl. The compounds with from 0-2 groups were isolated and characterized. The fraction with degree of phenyl substitution equal to 2, a mixture of cis and trans 1,2-; 1,3-; and 1,4 isomers, was isolated in 32 percent yield. Pure 1,4 diphenyldecamethylcyclohexasilane was isolated from the mixed diphenyl compounds and characterized. Diphenyldecamethylcyclohexasilanes were dephenylated to dichlorodecamethylcyclohexasilanes by treating with H2SO4.NH4Cl in benzene. The latter were purified and polymerized by reacting with sodium in toluene. The polymers were characterized by HPGPC, elemental analysis, proton NMR, and IR. Thermogravimetric analyses were carried out on the polymers. As the yield of residual SiC was low, polymers were heat treated to increase the residual char yield. As high as 51.52 percent residual char yield was obtained in one case

Disrupted seasonal clockwork in the population dynamics of a freshwater copepod by climate warming

Life history responses are expected to accompany climate warming, yet little is known how long-term effects of climate and environmental change affect the seasonal dynamics of planktonic organisms. We used an historical data set from Lake Washington (U.S.A.) to quantify population responses of a calanoid copepod (Leptodiaptomus ashlandi) to long-term changes in temperature and resource availability and explore potential mechanisms for the responses. Increasing water temperatures (annual mean increase of 1.5 degrees C in the upper 10-m water volume) and longer stratification periods (about 4 weeks) were observed between 1962 and 2005, coincident with a pronounced decline in Leptodiaptomus densities. However, production was maintained because of an increase in the production to biomass ratio and a life cycle shift in Leptodiaptomus from an annual to a 6-month cycle. Cross-wavelet analyses demonstrated that the annual thermal forcing of copepod recruitment observed during the first two decades of the study weakened substantially, leading to more stochastic population dynamics during the past two decades. This shift from one to two generations per year was most likely produced by a longer and warmer growing period combined with changing fluctuations in resource (phytoplankton) availability. Climate change can lead to higher-frequency voltinism in ectothermic organisms and to temporal reorganization of their population dynamics

Genetic and Neuroanatomical Support for Functional Brain Network Dynamics in Epilepsy

Focal epilepsy is a devastating neurological disorder that affects an overwhelming number of patients worldwide, many of whom prove resistant to medication. The efficacy of current innovative technologies for the treatment of these patients has been stalled by the lack of accurate and effective methods to fuse multimodal neuroimaging data to map anatomical targets driving seizure dynamics. Here we propose a parsimonious model that explains how large-scale anatomical networks and shared genetic constraints shape inter-regional communication in focal epilepsy. In extensive ECoG recordings acquired from a group of patients with medically refractory focal-onset epilepsy, we find that ictal and preictal functional brain network dynamics can be accurately predicted from features of brain anatomy and geometry, patterns of white matter connectivity, and constraints complicit in patterns of gene coexpression, all of which are conserved across healthy adult populations. Moreover, we uncover evidence that markers of non-conserved architecture, potentially driven by idiosyncratic pathology of single subjects, are most prevalent in high frequency ictal dynamics and low frequency preictal dynamics. Finally, we find that ictal dynamics are better predicted by white matter features and more poorly predicted by geometry and genetic constraints than preictal dynamics, suggesting that the functional brain network dynamics manifest in seizures rely on - and may directly propagate along - underlying white matter structure that is largely conserved across humans. Broadly, our work offers insights into the generic architectural principles of the human brain that impact seizure dynamics, and could be extended to further our understanding, models, and predictions of subject-level pathology and response to intervention

Fingerprints of biocomplexity: Taxon‐specific growth of phytoplankton in relation to environmental factors

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/110012/1/lno2004494part21446.pd

Life at high Deborah number

In many biological systems, microorganisms swim through complex polymeric fluids, and usually deform the medium at a rate faster than the inverse fluid relaxation time. We address the basic properties of such life at high Deborah number analytically by considering the small-amplitude swimming of a body in an arbitrary complex fluid. Using asymptotic analysis and differential geometry, we show that for a given swimming gait, the time-averaged leading-order swimming kinematics of the body can be expressed as an integral equation on the solution to a series of simpler Newtonian problems. We then use our results to demonstrate that Purcell's scallop theorem, which states that time-reversible body motion cannot be used for locomotion in a Newtonian fluid, breaks down in polymeric fluid environments

Arginine-rich peptides destabilize the plasma membrane, consistent with a pore formation translocation mechanism of cell-penetrating peptides

Recent molecular-dynamics simulations have suggested that the arginine-rich HIV Tat peptides translocate by destabilizing and inducing transient pores in phospholipid bilayers. In this pathway for peptide translocation, Arg residues play a fundamental role not only in the binding of the peptide to the surface of the membrane, but also in the destabilization and nucleation of transient pores across the bilayer. Here we present a molecular-dynamics simulation of a peptide composed of nine Args (Arg-9) that shows that this peptide follows the same translocation pathway previously found for the Tat peptide. We test experimentally the hypothesis that transient pores open by measuring ionic currents across phospholipid bilayers and cell membranes through the pores induced by Arg-9 peptides. We find that Arg-9 peptides, in the presence of an electrostatic potential gradient, induce ionic currents across planar phospholipid bilayers, as well as in cultured osteosarcoma cells and human smooth muscle cells. Our results suggest that the mechanism of action of Arg-9 peptides involves the creation of transient pores in lipid bilayers and cell membranes.Facultad de Ciencias Exacta

Simulation Study of Sulfonate Cluster Swelling in Ionomers

We have performed simulations to study how increasing humidity affects the structure of Nafion-like ionomers under conditions of low sulfonate concentration and low humidity. At the onset of membrane hydration, the clusters split into smaller parts. These subsequently swell, but then maintain constant the number of sulfonates per cluster. We find that the distribution of water in low-sulfonate membranes depends strongly on the sulfonate concentration. For a relatively low sulfonate concentration, nearly all the side-chain terminal groups are within cluster formations, and the average water loading per cluster matches the water content of membrane. However, for a relatively higher sulfonate concentration the water-to-sulfonate ratio becomes non-uniform. The clusters become wetter, while the inter-cluster bridges become drier. We note the formation of unusual shells of water-rich material that surround the sulfonate clusters.Comment: 24 pages, 15 figure