Biotechnology for fats and oils: new oxygenated fatty acids

Abstract

Among the three groups of natural products (starch, protein and fat), fat and oil are the most under-investigated. The US has a large amount of surplus soybean oil annually, and using vegetable oils or their component fatty acids as starting material provides a new opportunity for bioindustry. Vegetable oils are relatively inexpensive and can be used to manufacture value-added products such as oxygenated oils and fatty acids. Oxygenated fatty acids are common in nature and are important industrial materials. They exist both in mammals and plants. Microorganisms oxidize fatty acids either at the terminal carbon or inside of the acyl chain to produce hydroxyl or keto fatty acids. In our continuing effort to produce value-added products from vegetable oils, we discovered more than one dozen novel oxygenated fatty acids through biotransformation. Microbial hydratase is a carbon 10 positional specific enzyme. Many of these new oxygenated fatty acids possess physiological activities and can be used as biomedicals, in addition to their known applications such as specialty chemicals. The position of hydroxyl groups on the fatty acyl carbon chain plays an important role in the activity against certain specific plant pathogenic fungi. Bacillus megaterium ALA2 converted polyunsaturated fatty acids (PUFA) in different ways. It converted omega-6 PUFAs to a mixture of diepoxy bicyclic, tetrahydrofuranyl rings, and/or trihydroxy groups in their molecules while the products from omega-3 PUFAs produced only hydroxyl tetrahydrofuranyl ring products. The monooxygenase gene of strain ALA2 was sequenced and is a soluble, self-sufficient P450(BM-3) subclass that was highly homologous with the wild-type protein. This new enzyme also possessed a significant high homology in all of the expected reductase regions as well. Fat and oil represent an area with tremendous opportunity for new biotechnology to explore.

Regioselective Biocatalytic Hydroxylation of Fatty Acids by Cytochrome P450s

“…Whereas self-sufficient P450s show the highest turnover numbers and coupling efficiency up to now, fusion to redox partners or modern electron donor systems allow also other CYPs to run with increased efficiency [94,125,131,132]. Drawbacks of the CYP family are poor (regio-)selectivities, low productivities, uncoupling, and the dependence on NADPH as reducing agent [14,17,18]. The latter may be overcome by P450 peroxygenases, which utilize hydrogen peroxide as oxidant [23].…”

“…acting as antibiotic or anti-inflammatory [19]. A range of (R)-α-hydroxy fatty acids (C 14 -C 18 ) has shown antimicrobial activities against plant pathogenic organism such as Vibrio tyrogenuses [39], while (R)-α-and β-hydroxy fatty acids (C 10 -C 12 , and C 14 ) have shown antifungal activity against molds such as Aspergillus fumigatus, Penicillium commune and many more [17,[39][40][41]. Some β-hydroxy fatty acids (e.g.…”

“…However, low turnover rates, the requirement of complex electron transfer systems and cofactor regeneration complicate the synthetic application of P450s for the production of valuable fine chemicals and consequently more efficient family members are required for bulk applications [14,17,18].…”

Spatiotemporal changes in the Content and Metabolism of 9, 12, 13 – Trihydorxy-10(E)-Octadecenoic Acid in Tomato (<i>Solanum Lycopersicum</i> L. CV Balkonsar) fruits

“…Metabolic pathways involving 9,12,13-THODA have not yet been report in plant tissues. Notwithstanding, microbial transformations of other types of trihydroxy fatty acids into tetrahydrofuranyl fatty acids and bicyclical diepoxy fatty acids have already been reported (Hou, 2009;Hosokawa et al, 2003;Iwasaki et al, 2002). Indeed, tetrahydrofuranyl fatty acids are structurally close to known anticancer compounds (Kawagishi et al, 1990;Stadler et al, 1994) and diepoxy fatty acids could be used in biochemical and chemical industrial processes.…”

Production of 5,8-dihydroxy-9(Z)-octadecenoic acid from oleic acid by whole recombinant cells of Aspergillus nidulans expressing diol synthase

“…Hydroxyfatty acids exhibit higher reactivity, viscosity, solvent miscibility, and hydrophilicity than free fatty acids (Metzger and Bornscheuer 2006;Hou 2009). These reactive properties have facilitated hydroxyfatty acids to be exploited as starting materials for resins, waxes, nylons, plastics, lubricants, and cosmetics (Naughton 1974;Ogunniyi 2006), and as precursors in the synthesis of the flavor lactones .…”