A chemoenzymatic route to chiral siloxanes

An approach employing two enzymes—toluene dioxygenase and immobilized lipase B from Candida antarctica (N435)—was explored as a potential biocatalytic method for the coupling of chiral diols with siloxane species. Analysis of reaction mixtures using1H NMR spectroscopy suggested that up to 66% consumption of the siloxane starting materials had occurred. Oligomeric species were observed and chiral products from the coupling of a cyclic diol with a siloxane molecule were isolated and characterized by MALDI-ToF MS and GPC. Immobilized lipases from Rhizomucor miehei and Thermomyces lanuginosus were also explored as potential catalysts for the coupling reactions, however, their use only returned starting material

Synthesis of polyesters containing disiloxane subunits: Structural characterization, kinetics, and an examination of the thermal tolerance of Novozym-435

This paper reports the Novozym-435 mediated polymerization of disiloxane-containing polyester monomers under solvent-free conditions. The thermal tolerance of the immobilized enzyme was examined by conducting polymerization cycles over a temperature range of 35-150 °C. Increasing the temperature up to 100 °C afforded an increase in the apparent second order rate constant. Residual activity was measured using the production of octyl palmitate. The enzyme was shown to retain on average greater than 90% of its residual activity regardless of the polymerization temperature. This prompted a study of the long term thermal tolerance of the biocatalyst in which it was determined that over ten reaction cycles there was a significant decrease in the initial polymerization rate, but no change in the degree of monomer conversion after 24 h. The disiloxane containing polyesters were characterized using nuclear magnetic resonance spectroscopy and Fourier-transform infrared spectroscopy. Differential scanning calorimetry was used to determine the thermal properties of the disiloxane-containing polyesters. © 2012 Elsevier B.V. All rights reserved

Consensus statement understanding health and malnutrition through a systems approach:the ENOUGH program for early life

Nutrition research, like most biomedical disciplines, adopted and often uses experimental approaches based on Beadle and Tatum's one gene-one polypeptide hypothesis, thereby reducing biological processes to single reactions or pathways. Systems thinking is needed to understand the complexity of health and disease processes requiring measurements of physiological processes, as well as environmental and social factors, which may alter the expression of genetic information. Analysis of physiological processes with omics technologies to assess systems' responses has only become available over the past decade and remains costly. Studies of environmental and social conditions known to alter health are often not connected to biomedical research. While these facts are widely accepted, developing and conducting comprehensive research programs for health are often beyond financial and human resources of single research groups. We propose a new research program on essential nutrients for optimal underpinning of growth and health (ENOUGH) that will use systems approaches with more comprehensive measurements and biostatistical analysis of the many biological and environmental factors that influence undernutrition. Creating a knowledge base for nutrition and health is a necessary first step toward developing solutions targeted to different populations in diverse social and physical environments for the two billion undernourished people in developed and developing economies