Structure sensitivity of reactions between cyclopropane and hydrogen on supported ruthenium catalysts

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/26492/1/0000028.pd

The role of the zeolite in the hydrogenolysis of C2 and C3 hydrocarbons on RuNaY catalysts

The catalytic properties for the hydrogenolysis of ethane, propane and cyclopropane of a series of highly dispersed RuNaY catalysts have been investigated. These catalysts have activities and selectivities for ethane and propane hydrogenolysis similar to other supported ruthenium catalysts. However, the activity of the RuNaY for cyclopropane hydrogenolysis is much higher than that of Ru on conventional oxide supports, while the selectivities remain in a range expected for well-dispersed ruthenium. The increase in activity for the RuNaY catalysts is due mainly to the presence of highly dispersed Ru particles made possible by the zeolite support. A destabilization of the cyclopropane ring by the electrostatic field of the zeolite, however, does not seem to contribute significantly to the observed rate increase. It appears that the ring opening of cyclopropane and the hydrogenolysis of cyclopropane to ethane and methane have a common intermediate, the formation of which is rate determining for both reactions. The discovery that on Ru the ring opening of cyclopropane is structure sensitive is surprising since this reaction is generally considered as a classic example for structure insensitivity.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/26286/1/0000371.pd

CO hydrogenation catalyzed by alumina-supported osmium: Particle size effects

Alumina-supported catalysts were prepared by conventional aqueous impregnation with [H2OsCl6] and by reaction of organoosmium clusters {[Os3(CO)12], [H4Os4(CO)12], and [Os6(CO)18]} with the support. The catalysts were tested for CO hydrogenation at 250-325 [deg]C and 10 atm, the products being Schulz-Flory distributions of hydrocarbons with small yields of dimethyl ether. The fresh and used catalysts were characterized by infrared spectroscopy and high-resolution transmission electron microscopy. The catalyst prepared from [H2OsCl6] had larger particles of Os (~70 A). The cluster-derived catalysts initially consisted of molecular clusters on the support; the used catalysts contained small Os aggregates (typically 10-20 A in diameter). The catalytic activity for hydrocarbon formation increased with increasing Os aggregate size, but the activity for dimethyl ether formation was almost independent of aggregate size. The hydrocarbon synthesis was evidently catalyzed by the Os aggregates, and the ether synthesis was perhaps catalyzed by mononuclear Os Complexes.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/25555/1/0000097.pd

Allele specific repair of splicing mutations in cystic fibrosis through AsCas12a genome editing.

Funder: Fondazione Fibrosi Cistica - FFC#1/2017Cystic fibrosis (CF) is an autosomal recessive disease caused by mutations in the CFTR gene. The 3272-26A>G and 3849+10kbC>T CFTR mutations alter the correct splicing of the CFTR gene, generating new acceptor and donor splice sites respectively. Here we develop a genome editing approach to permanently correct these genetic defects, using a single crRNA and the Acidaminococcus sp. BV3L6, AsCas12a. This genetic repair strategy is highly precise, showing very strong discrimination between the wild-type and mutant sequence and a complete absence of detectable off-targets. The efficacy of this gene correction strategy is verified in intestinal organoids and airway epithelial cells derived from CF patients carrying the 3272-26A>G or 3849+10kbC>T mutations, showing efficient repair and complete functional recovery of the CFTR channel. These results demonstrate that allele-specific genome editing with AsCas12a can correct aberrant CFTR splicing mutations, paving the way for a permanent splicing correction in genetic diseases

Comparative Genomic Analysis of Drosophila melanogaster and Vector Mosquito Developmental Genes

Genome sequencing projects have presented the opportunity for analysis of developmental genes in three vector mosquito species: Aedes aegypti, Culex quinquefasciatus, and Anopheles gambiae. A comparative genomic analysis of developmental genes in Drosophila melanogaster and these three important vectors of human disease was performed in this investigation. While the study was comprehensive, special emphasis centered on genes that 1) are components of developmental signaling pathways, 2) regulate fundamental developmental processes, 3) are critical for the development of tissues of vector importance, 4) function in developmental processes known to have diverged within insects, and 5) encode microRNAs (miRNAs) that regulate developmental transcripts in Drosophila. While most fruit fly developmental genes are conserved in the three vector mosquito species, several genes known to be critical for Drosophila development were not identified in one or more mosquito genomes. In other cases, mosquito lineage-specific gene gains with respect to D. melanogaster were noted. Sequence analyses also revealed that numerous repetitive sequences are a common structural feature of Drosophila and mosquito developmental genes. Finally, analysis of predicted miRNA binding sites in fruit fly and mosquito developmental genes suggests that the repertoire of developmental genes targeted by miRNAs is species-specific. The results of this study provide insight into the evolution of developmental genes and processes in dipterans and other arthropods, serve as a resource for those pursuing analysis of mosquito development, and will promote the design and refinement of functional analysis experiments

Global Soil Moisture Patterns Observed by Space Borne Microwave Radiometers and Scatterometers

Within the scope of the upcoming launch of a new water related satellite mission (SMOS) a global evaluation study was performed on two available global soil moisture products. ERS scatterometer surface wetness data was compared to AMSR-E soil moisture data. This study pointed out a strong similarity between both products in sparse to moderate vegetated regions with an average correlation coefficient of 0.83. Low correlations were found in densely vegetated areas and deserts. The low values in the vegetated regions can be explained by the limited soil moisture retrieval capabilities over dense vegetation covers. Soil emission is attenuated by the canopy and tends to saturate the microwave signal with increasing vegetation density, resulting in a decreased sensor sensitivity to soil moisture variations. It is expected that the new low frequency satellite mission (SMOS) will obtain soil moisture products with a higher quality in these regions. The low correlations in the desert regions are likely due to volume scattering or to the dielectric dynamics within the soil. The volume scattering in dry soils causes a higher backscatter under very dry conditions than under conditions when the sub-surface soil layers are somewhat wet. In addition, at low moisture levels the dielectric constant has a reduced sensitivity in response to changes in the soil moisture content. At a global scale the spatial correspondence of both products is high and both products clearly distinguish similar regions with high seasonal and inter annual variations. Based on the global analyses we concluded that the quality of both products was comparable and in the sparse to moderate vegetated regions both products may be beneficial for large scale validation of SMOS soil moisture. Some limitations of the studied products are different, pointing to significant potential for combining both products into one superior soil moisture data set. © The Author(s) 2008

\u3ci\u3eGregarina niphandrodes\u3c/i\u3e (Eugregarinorida: Septatorina): Oocyst Surface Architecture

The surface architecture of oocysts produced by Gregarina niphandrodes (Eugregarinorida) from Tenebrio molitor,/i\u3e adults (Coleoptera: Tenebrionidae) as revealed by scanning electron microscopy is reported. Gametocysts were allowed to dehisce on 15-mm, round cover glasses; the cover glasses with their oocysts chains were then mounted on stubs without further processing, and sputter-coated with 20-nm gold-palladium. Scanning electron microscopy was performed at 10-15 kV with a Hitachi 3000N SEM. Oocysts retained their characteristic shapes as reported in the original species description but showed longitudinal ridges of relatively uniform height, width, and spacing, in separate fields on either side of a central equatorial bulge in the oocysts. There was no ultrastructural evidence of an enclosing external sheath holding the oocysts in a chain. Oocyst ends were flared slightly, and the chain itself was twisted, with adjacent oocysts offset slightly from one another. This article now provides an additional set of structural characters potentially useful in gregarine systematics