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Catalytic, asymmetric alpha-chlorination of acid halides.

We present a full account of a tandem catalytic, asymmetric chlorination/esterification process that produces highly optically enriched alpha-chloroesters from inexpensive, commercially available acid halides using cinchona alkaloid derivatives as catalysts and polychlorinated quinones as halogenating agents. We have performed kinetics and control experiments to investigate the reaction mechanism and establish conditions under which the reactions can be best performed. We have developed NaH and NaHCO3 shuttle base systems as the easiest and most cost-effective ways of conducting the reactions, rendering the methodology economically competitive with known chiral halogenation procedures. We have also demonstrated the utility of our reactions by converting the products to synthetically useful derivatives.

Journal Article↗

Metabolic engineering of Arabidopsis and Brassica for poly(3-hydroxybutyrate-co-3-hydroxyvalerate) copolymer production.

Poly(hydroxyalkanoates) are natural polymers with thermoplastic properties. One polymer of this class with commercial applicability, poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) can be produced by bacterial fermentation, but the process is not economically competitive with polymer production from petrochemicals. Poly(hydroxyalkanoate) production in green plants promises much lower costs, but producing copolymer with the appropriate monomer composition is problematic. In this study, we have engineered Arabidopsis and Brassica to produce PHBV in leaves and seeds, respectively, by redirecting the metabolic flow of intermediates from fatty acid and amino acid biosynthesis. We present a pathway for the biosynthesis of PHBV in plant plastids, and also report copolymer production, metabolic intermediate analyses, and pathway dynamics.

Acyl Coenzyme A↗

Polyhydroxyalkanoate (PHA) hemeostasis: the role of PHA synthase.

Polyhydroxyalkanoates (PHAs) are biodegradable polymers with properties of thermoplastics Production of these polymers in an economically competitive fashion via bioengineering requires an understanding of the biosynthetic pathway and its regulation. This review summarizes our current knowledge of the mechanism of the class I and III PHA synthases: the initiation, elongation and termination processes. It also summarizes our current understanding of the phase transition from soluble substrates (coenzyme A esters of beta-hydroxyalkanoates) to insoluble granules and our understanding of the requirement for a transcription factor, phasin proteins, and depolymerases in PHA homeostasis.

Acyltransferases↗

Preparative deracemization of unnatural amino acids.

Unnatural amino acids are a growing class of intermediates required for pharmaceuticals, agrochemicals and other industrial products. However, no single method has proven sufficiently versatile to prepare these compounds broadly at scale. To address this need, we have developed a general chemoenzymatic process to prepare enantiomerically pure L- and D-amino acids in high yield by deracemization of racemic starting materials. This method involves the concerted action of an enantioselective oxidase biocatalyst and a non-selective chemical reducing agent to effect the stereoinversion of one enantiomer and can result in an enantiomeric excess of >99% from the starting racemate, and product yields of over 90%. This approach compares very favourably with resolution processes, which have a maximum single-pass yield of 50%. We have developed efficient methods to adapt the process towards new target compounds and to optimize key factors that influence process efficiency and offer competitive economics at scale.

Amino Acids↗

The pricing of nursing care.

Despite the poor performance of the general economy, the health care industry in Australia has experienced constant growth for several decades. Overall, Australia's expenditure on health is relatively high and, with an increasingly aged population, this expenditure is not likely to decrease. With the current concerns over cost-containment in the health sector it is important to assess the value of nursing care in economic terms. This paper explores the issue of valuing of nursing care within the framework of the Australian Health Care System. Questions are posed of nurses as to whether they are prepared to confront the realities of the health care arena and whether they are ready to value nursing practice in terms of economic value. As well as answering these questions, the paper argues that nursing costs are not sufficiently reimbursed under the current Australian health benefits, and that this poor estimation of the worth of health care may stem from the historical and social influences of nursing and the care provided by nurses. The paper concludes that the Australian health care system is clearly no longer static and that the public cannot afford to support the costs associated with a growing health care industry. Moreover, nursing can no longer afford not to be viewed as an entity in it's own right. A greater awareness of nursing's output will result if organisational or institutional changes are encouraged for the benefit of the Australian society, as a whole, as well as for the nursing profession.

Attitude to Health↗

Physician DRGs.

DRG-based reimbursement for inpatient services is an option currently being considered by federal policy makers, but little is known about how physician DRGs might work. We performed simulations of potential impacts, using Medicare claims from four states. Although physician-related inpatient costs associated with surgical DRGs were quite homogeneous, those associated with medical admissions varied dramatically. This suggests that DRG payment could be a lottery, with inequitable losses for some physicians and windfall gains for others. Potential gains and losses were also found to be systematically related to the specialty of the attending physician. General practitioners and ophthalmologists would gain financially on average, whereas medical specialists and some surgical specialists would incur net losses. These differences may be due to the triaging of more seriously ill patients within a given DRG to certain specialists.

Costs and Cost Analysis↗