Synthesis of 3,3-Dimethylbutanol and 3,3-Dimethylbutanal, Important Intermediates in the Synthesis of Neotame

It has been shown that some N-alkyl derivatives of Aspartame (1) are enhanced sweetening agents [1]. In particular, the 3,3-dimethylbutyl derivative, 2, (Neotame) is about 70?times sweeter than Aspartame. With this in mind a research program directed toward the synthesis of 3,3-dimethylbutanal (3) was begun. The first phase of this research involved the synthesis of 3,3-dimethylbutanol (4) by the acid catalyzed alkylation of isobutene with ethylene to give the sulfate ester [2] which was readily hydrolyzed to the alcohol, 4, in isolated yields in the 70?C75?% range. It was found that the most efficient method for the conversion of 4 to the aldehyde, 3, was by a vapor phase dehydrogenation over a copper catalyst. The effect which the reaction variables have on the production of 4 will be discussed. This will include factors such as the ethylene pressure, the acid/isobutene ratio, the use of a hydrocarbon solvent, the reaction temperature and the mode of addition of the isobutene. The discussion of the dehydrogenation procedure will include the nature of the catalyst used and the reaction parameters needed to maximize the formation of 3 and keeping the amount of the over-oxidation carboxylic acid product below 1?%.     

Agro-ecological nitrogen management in soils vulnerable to nitrate leaching: a case study in the Lower Suwannee Watershed

Environmental benefits associated with reduced rates of nitrogen (N) application, while maintaining economically optimum yields have economic and social benefits. Although N is an indispensable plant nutrient, residual soil N could leach out to contaminate groundwater and surface water resources, particularly in sandy soils. A 2-year field study was conducted in an established bermudagrass (Cynodon dactylon) pasture in the Lower Suwannee Watershed, Florida, to evaluate N application rates on forage yield, forage quality, and nitrate (NO₃-N) leaching in rapidly permeable upland sandy soils. Four N application rates (30, 50, 70, and 90 kg N ha⁻¹ harvest⁻¹) corresponding to 0.33, 0.55, 0.77 and IX, respectively, of recommended N rate (90 kg N ha⁻¹ harvest⁻¹) for bermudagrass hay production in Florida were evaluated vis-à-vis an unfertilized (0 N) control. Suction cups were installed near the center of each plot at two depths (30 and 100 cm) to monitor NO₃-N leaching. The grass was harvested at 28 days intervals to determine dry matter yield, N uptake, and herbage nutritive value. Nitrogen application at the recommended rate produced the greatest total dry matter yield (~18.4 Mg ha⁻¹ year⁻¹), but a modeled economically optimum N rate of ~57 kg N ha⁻¹ harvest⁻¹ (~60% of the recommended N rate) projected an average dry matter yield of ~17.3 Mg ha⁻¹ year⁻¹, which represents >90% of the observed maximum yield. Nitrogen application increased nutritive quality of the grass, but increases in N application rate above 30 kg N ha⁻¹ did not result in significant increases in in vitro digestible organic matter concentration, and tissue crude protein was not significant above 50 kg N ha⁻¹. Across the sampling period, treatments with N rates ≤50 kg N ha⁻¹ harvest⁻¹ had leachate NO₃-N concentration below the maximum contaminant limit of <10 mg l⁻¹. Conversely, applying N at rates ≥70 kg N ha⁻¹ harvest⁻¹ resulted in leachate N concentration that exceeded the maximum contaminant limit, and suggest high risk of impacting groundwater quality, if such rates are applied to soils with coarse (sand) textures. The study demonstrates that recommendation of a single N application rate may not be appropriate under all agro-climatic conditions and, thus, a site-specific evaluation of best N management strategy is critical.     

S-band operation of SiC power MESFET with 20 W (4.4 W/mm) output power and 60% PAE

Previous efforts have revealed instabilities in standard SiC MESFET device electrical characteristics, which have been attributed to charged surface states. This work describes the use of an undoped "spacer" layer on top of a SiC MESFET to form a "buried-channel" structure where the active current carrying channel is removed from the surface. By using this approach, the induced surface traps are physically removed from the channel region, such that the depletion depth caused by the unneutralized surface states cannot reach the conductive channel. This results in minimal RF dispersion ("gate lag") and, thus, improved RF performance. Furthermore, the buried-channel approach provides for a relatively broad and uniform transconductance (G/sub m/) with gate bias (V/sub gs/), resulting in higher efficiency MESFETs with improved linearity and lower signal distortion. SiC MESFETs having 4.8-mm gate periphery were fabricated using this buried-channel structure and were measured to have an output power of 21 W (P/sub out//spl sim/4.4 W/mm), 62% power added efficiency, and 10.6 dB power gain at 3 GHz under pulse operation. When operated at continuous wave, similar 4.8-mm gate periphery SiC MESFETs produced 9.2 W output power (P/sub out//spl sim/2 W/mm), 40% PAE, and /spl sim/7 dB associated gain at 3 GHz.     

Catalytic defects in mutants of class II histidyl-tRNA synthetase from Salmonella typhimurium previously linked to decreased control of histidine biosynthesis regulation

The expression of histidine biosynthetic genes in enteric bacteria is regulated by an attenuation mechanism in which the level of histidyl-tRNA serves as a key sensor of the intracellular histidine pool. Among the early observations that led to the formation of this model for Salmonella typhimurium were the identification of mutants in the gene (hisS) encoding histidyl-tRNA synthetase. We report here the detailed biochemical characterization of five of these S. typhimurium bradytrophic mutants isolated by selection for resistance to histidine analogs, including identification of the deduced amino acid substitutions and determination of the resulting effects on the kinetics of adenylation and aminoacylation. Using the crystal structure of the closely related Escherichia coli histidyl-tRNA synthetase (HisRS) as a guide, two mutants were mapped to a highly conserved proline residue in motif 2 (P117S, P117Q), and were correlated with a fivefold decrease in the kcat for the pyrophosphate exchange reaction, as well as a tenfold increase in the Km for tRNA in the aminoacylation reaction. Another mutant substitution (A302T) mapped to a residue adjacent to the histidine binding pocket, leading to a tenfold increase in Km for histidine in the pyrophosphate exchange reaction. The remaining two mutants (S167F, N254T) substitute residues in or directly adjacent to the hinge region, which joins the insertion domain between motif 2 and motif 3 to the catalytic core, and cause the Km for tRNA to increase four- to tenfold. The kinetic analysis of these mutants establishes a direct link between critical interactions within the active site of HisRS and regulation of histidine biosynthesis, and provides further evidence for the importance of local conformational changes during the catalytic cycle.     

Effect of betaine on the growth performance of chicks inoculated with mixed cultures of avian Eimeria species and on invasion and development of Eimeria tenella and Eimeria acervulina in vitro and in vivo

At 7 d postinoculation (DPI) with a mixed culture of avian Eimeria species, 21-d-old chicks maintained in batteries and floor pens on a diet containing 0.15% (3 lb/ton) betaine plus 66 ppm (60 g/ton) salinomycin were significantly heavier and had significantly lower feed conversion ratios and mortality than chicks fed diets containing 0.15% betaine or 66 ppm salinomycin alone, or the control diet. At 31 DPI, when the chicks were 45 d old, the differences between the diet groups were not as great as at 7 DPI. In vitro, except at high concentrations, betaine was nontoxic to sporozoites of Eimeria tenella or Eimeria acervulina and had little effect on their invasion and development in cultured cells. In vivo, invasion by E. tenella and E. acervulina sporozoites was significantly reduced in all chicks fed diets containing betaine or salinomycin compared with that in control chicks. There was a significant interaction between betaine and salinomycin that impacted on invasion by both species. Overall development of E. tenella did not appear to be adversely affected by addition of betaine to diets containing salinomycin. Conversely, development of E. acervulina was reduced in chicks fed diets containing 0.075% (1.5 lb/ton) betaine plus 66 ppm salinomycin as compared with that in chicks fed salinomycin alone.     

Anchored Wilkinson Catalyst: Hydrogenation of β Pinene

The hydrogenation of β pinene over homogeneous and anchored Wilkinson’s catalysts was studied. Phosphotungstic acid was used to anchor the Wilkinson catalyst to an alumina support by an interaction between the heteropoly acid and the rhodium atom of the complex. The hydrogenation of β pinene over the anchored catalyst was accompanied by some isomerization to α-pinene which was subsequently hydrogenated along with the β pinene to the pinanes with selectivities to the cis (endo) pinane in the 85–88 % range at near 100 % conversion. With the homogeneous Wilkinson catalyst an 88 % selectivity to cis pinane was also observed but only at 82 % conversion. The use of a 1 % Rh/Al₂O₃ catalyst for this hydrogenation gave some unexpected results. There was a facile isomerization to α pinene which was not hydrogenated further. The reaction stopped at about 30 % conversion at which time the cis and trans pinanes were present in near equal amounts in about 16–18 % yields.

     

Inducible nitric oxide synthase expression in coronary arteries of transplanted human hearts with accelerated graft arteriosclerosis

In the vast majority of burned patients, the injury is limited to the skin and superficial subcutaneous tissue, and the vasculature of the deeper fascia is spared. This fact encouraged me to design a flap in which the burned scar tissue is employed. The island fasciocutaneous flap is based only on the proximal septocutaneous perforators of the radial artery. The flap is used to resurface the anterior as well as the lateral burned cubital fossa after excision of the scar tissue and release of contracture. An anatomic study as well as clinical approach has been conducted.