Mechanistic investigations of bipyrimidine-promoted palladium-catalyzed allylic acetoxylation of olefins

Several pyridine-like ligands were found to improve Pd(OAc)2-catalyzed allylic oxidation of allylbenzene to cinnamyl acetate by p-benzoquinone in acetic acid. The best ligand examined, bipyrimidine, was used to identify the catalyst precursor for this system, (bipyrimidine)Pd(OAc)2, which was fully characterized. Mechanistic studies suggest the reaction takes place through disproportionation of (bipyrimidine)Pd(OAc)2 to form a bipyrimidine-bridged dimer, which reacts with olefin to form a Pd^II-olefin adduct, followed by allylic C–H activation to produce (η^3-allyl)Pd^II species. The (η^3-allyl)Pd^II intermediate undergoes a reversible acetate attack to generate a Pd^0-(allyl acetate) adduct, which subsequently reacts with p-benzoquinone to release allyl acetate and regenerate (bipyrimidine)Pd(OAc)2. No KIE is observed for the competition experiment between allylbenzene-d0 and allylbenzene-d5 (CD2=CDCD2C6H5), suggesting that allylic C–H activation is not rate-determining. Catalytic allylic acetoxylations of other terminal olefins as well as cyclohexene were also effected by (bipyrimidine)Pd(OAc)2

Development of a thermal acoustical aircraft insulation material

A process was developed for fabricating a light weight foam suitable for thermal and acoustical insulation in aircraft. The procedures and apparatus are discussed, and the foam specimens are characterized by numerous tests and measurements

ST-Producing E. coli Oppose Carcinogen-Induced Colorectal Tumorigenesis in Mice.

There is a geographic inequality in the incidence of colorectal cancer, lowest in developing countries, and greatest in developed countries. This disparity suggests an environmental contribution to cancer resistance in endemic populations. Enterotoxigenic bacteria associated with diarrheal disease are prevalent in developing countries, including enterotoxigenic E. coli (ETEC) producing heat-stable enterotoxins (STs). STs are peptides that are structurally homologous to paracrine hormones that regulate the intestinal guanylyl cyclase C (GUCY2C) receptor. Beyond secretion, GUCY2C is a tumor suppressor universally silenced by loss of expression of its paracrine hormone during carcinogenesis. Thus, the geographic imbalance in colorectal cancer, in part, may reflect chronic exposure to ST-producing organisms that restore GUCY2C signaling silenced by hormone loss during transformation. Here, mice colonized for 18 weeks with control E. coli or those engineered to secrete ST exhibited normal growth, with comparable weight gain and normal stool water content, without evidence of secretory diarrhea. Enterotoxin-producing, but not control, E. coli, generated ST that activated colonic GUCY2C signaling, cyclic guanosine monophosphate (cGMP) production, and cGMP-dependent protein phosphorylation in colonized mice. Moreover, mice colonized with ST-producing E. coli exhibited a 50% reduction in carcinogen-induced colorectal tumor burden. Thus, chronic colonization with ETEC producing ST could contribute to endemic cancer resistance in developing countries, reinforcing a novel paradigm of colorectal cancer chemoprevention with oral GUCY2C-targeted agents

Thermal/acoustical aircraft insulation material

Attempts made to improve the acoustical properties of low density Fiberfrax foam, an aircraft insulation material, are reported. Characterizations were also made of the physical and thermal properties. Two methods, optimization of fiber blend composition and modification of the foam fabrication process, were examined as possible means of improving foam acoustics. Flame impingement tests were also made; results show performance was satisfactory

Packet equalisation in PONs using adjustable gain-clamped semiconductor optical amplifiers (AGC-SOA)

The past ten years have witnessed a dramatic growth in the delivery of high bandwidth services through Passive Optical Networks (PONs), directly to the home or to the kerb. The bursty nature of upstream traffic in a PON (from the user to Optical Network Unit, ONU) combined with a wide dynamic range of signal strength (-15dB to -28dB the difference between a very close Optical Network Terminal (ONT) with a small split ratio and a distant ONT with a high split ratio), places severe demands on the burst mode receiver at the ONU. We report here on an adjustable gain-clamped semiconductor optical amplifier (AGC-SOA) designed to maximize the output saturated power while adjusting gain to regulate the power differences between packets without loss of linearity. This device is shown to be able to modulate gain at rates that are compatible with packet to packet equalisation. Through theoretical analysis coupled with experimental verification, this paper demonstrates for the first time that this is entirely feasible