Low Catalyst Loadings in Olefin Metathesis: Synthesis of Nitrogen Heterocycles by Ring-Closing Metathesis

A series of ruthenium catalysts have been screened under ring-closing metathesis (RCM) conditions to produce five-, six-, and seven-membered carbamate-protected cyclic amines. Many of these catalysts demonstrated excellent RCM activity and yields with as low as 500 ppm catalyst loadings. RCM of the five-membered carbamate series could be run neat, the six-membered carbamate series could be run at 1.0 M, and the seven-membered carbamate series worked best at 0.2−0.05 M

Concise Syntheses of Insect Pheromones Using Z-Selective Cross Metathesis

The use of insect sex pheromones to limit specifically targeted pest populations has gained increasing popularity as a viable, safe, and environmentally friendly alternative to insecticides. While broad-spectrum insecticides are toxic compounds that have been shown to adversely affect human health,[1] extensive studies have shown that insect pheromones are nontoxic and safe for human consumption at the levels used in pest control practices.[2] Female sex pheromones are mainly employed in pest control in a process termed mating disruption. This involves dispersing pheromones over a large area, overloading the sensory organs of male insects and preventing them from locating and mating with females who are releasing a much smaller amount of the same pheromone blends; this strategy has proven to reduce specific insect populations dramatically.[3] To date, the United States Environmental Protection Agency (EPA) has approved approximately twenty lepidopteran female sex pheromones as active ingredients for pest control.[2

Influence of Post-harvest Circulatory Rinse on Tenderness and Objective Color of Cow Striploin Steaks

The objective of this study was to compare the effect of a post-harvest rinse of an isotonic solution through the circulatory system on tenderness of steaks from cows

Investigation on the Use of a FLIR (Forward Looking Infrared) Camera to Detect Relationships Between Internal and Surface Temperatures of Beef Carcasses During Chilling

The objective of this study was to collect preliminary data on the efficacy of using thermal imaging technology as a means to assess beef carcass chilling

Double quantum dot with tunable coupling in an enhancement-mode silicon metal-oxide semiconductor device with lateral geometry

We present transport measurements of a tunable silicon metal-oxide-semiconductor double quantum dot device with lateral geometry. Experimentally extracted gate-to-dot capacitances show that the device is largely symmetric under the gate voltages applied. Intriguingly, these gate voltages themselves are not symmetric. Comparison with numerical simulations indicates that the applied gate voltages serve to offset an intrinsic asymmetry in the physical device. We also show a transition from a large single dot to two well isolated coupled dots, where the central gate of the device is used to controllably tune the interdot coupling.Comment: 4 pages, 3 figures, to be published in Applied Physics Letter

Influence of Beef Production System on Calpain-1 Autolysis and Troponin-T Degradation

The objective of this study was to determine the impact beef production systems utilizing different levels of growth promotant technology on calpain-1 autolysis and troponin-T degradation, which are measures of tenderness

Enhancement mode double top gated MOS nanostructures with tunable lateral geometry

We present measurements of silicon (Si) metal-oxide-semiconductor (MOS) nanostructures that are fabricated using a process that facilitates essentially arbitrary gate geometries. Stable Coulomb blockade behavior free from the effects of parasitic dot formation is exhibited in several MOS quantum dots with an open lateral quantum dot geometry. Decreases in mobility and increases in charge defect densities (i.e. interface traps and fixed oxide charge) are measured for critical process steps, and we correlate low disorder behavior with a quantitative defect density. This work provides quantitative guidance that has not been previously established about defect densities for which Si quantum dots do not exhibit parasitic dot formation. These devices make use of a double-layer gate stack in which many regions, including the critical gate oxide, were fabricated in a fully-qualified CMOS facility.Comment: 11 pages, 6 figures, 3 tables, accepted for publication in Phys. Rev.

Z-Selective Cross-Metathesis and Homodimerization of 3E-1,3-Dienes: Reaction Optimization, Computational Analysis, and Synthetic Applications

Olefin metathesis reactions with 3E-1,3-dienes using Z-selective cyclometalated ruthenium benzylidene catalysts are described. In particular, a procedure for employing 3E-1,3-dienes in Z-selective homodimerization and cross-metathesis with terminal alkenes is detailed. The reaction takes advantage of the pronounced chemoselectivity of a recently reported ruthenium-based catalyst containing a cyclometalated NHC ligand for terminal alkenes in the presence of internal E-alkenes. A wide array of commonly encountered functional groups can be tolerated, and only a small excess (1.5 equiv) of the diene coupling partner is required to achieve high yields of the desired internal E,Z-diene cross-metathesis product. Computational studies have been performed to elucidate the reaction mechanism. The computations are consistent with a diene-first pathway. The reaction can be used to quickly assemble structurally complex targets. The power of this cross-metathesis reaction is demonstrated by the concise syntheses of two insect pheromones

Probing Stereoselectivity in Ring-Opening Metathesis Polymerization Mediated by Cyclometalated Ruthenium-Based Catalysts: A Combined Experimental and Computational Study

The microstructures of polymers produced by ring-opening metathesis polymerization (ROMP) with cyclometalated Ru-carbene metathesis catalysts were investigated. A strong bias for a cis,syndiotactic microstructure with minimal head-to-tail bias was observed. In instances where trans errors were introduced, it was determined that these regions were also syndiotactic. Furthermore, hypothetical reaction intermediates and transition structures were analyzed computationally. Combined experimental and computational data support a reaction mechanism in which cis,syndio-selectivity is a result of stereogenic metal control, while microstructural errors are predominantly due to alkylidene isomerization via rotation about the Ru═C double bond