Biocatalytic Synthesis of Epoxy Resins from Fatty Acids as a Versatile Route for the Formation of Polymer Thermosets with Tunable Properties.

The work herein presented describes the synthesis and polymerization of series of bio-based epoxy resins prepared through lipase catalyzed transesterification. The epoxy-functional polyester resins with various architectures (linear, tri-branched, and tetra-branched) were synthesized through condensation of fatty acids derived from epoxidized soybean oil and linseed oil with three different hydroxyl cores under bulk conditions. The selectivity of the lipases toward esterification/transesterification reactions allowed the formation of macromers with up to 12 epoxides in the backbone. The high degree of functionality of the resins resulted in polymer thermosets with Tg values ranging from -25 to over 100 °C prepared through cationic polymerization. The determining parameters of the synthesis and the mechanism for the formation of the species were determined through kinetic studies by 1H NMR, SEC, and molecular modeling studies. The correlation between macromer structure and thermoset properties was studied through real-time FTIR measurements, DSC, and DMA.

Laccase oxidation and removal of toxicants released during combustion processes.

This study reports for the first time the ability of laccases adsorbed on cellulose acetate to eliminate toxicants released during combustion processes. Laccases directly oxidized and eliminated more than 40% w/v of 14 mM of 1,4-dihydroxybenzene (hydroquinone); 2-methyl-1,4-benzenediol (methylhydroquinone); 1,4-dihydroxy-2,3,5-trimethylbenzene (trimethylhydroquinone); 3-methylphenol (m-cresol); 4-methylphenol (p-cresol); 2-methylphenol (o-cresol); 1,3-benzenediol (resorcinol); 1,2-dihydroxybenzene (catechol); 3,4-dihydroxytoluene (4-methylcatechol) and 2-naphthylamine. Further, laccase oxidized 2-naphthylamine, hydroquinone, catechol, methylhydroquinone and methylcatechol were also able to in turn mediate the elimination of >90% w/v of toxicants which are per-se non-laccase substrates such as 3-aminobiphenyl; 4-aminobiphenyl; benz[a]anthracene; 3-(1-nitrosopyrrolidin-2-yl) pyridine (NNN); formaldehyde; 4-(methyl-nitrosamino-1-(3-pyridyl)-1-butanone (NNK); 2-butenal (crotonaldehyde); nitric oxide and vinyl cyanide (acrylonitrile). These studies demonstrate the potential of laccase immobilized on solid supports to remove many structurally different toxicants released during combustion processes. This system has great potential application for in situ removal of toxicants in the manufacturing, food processing and food service industries.