Lipid oxidation in n-3 fatty acid enriched Dutch style fermented sausages.

Dutch style fermented sausages were manufactured with a substitution of 10%, 15% and 20% of pork backfat by flaxseed oil and canola oil, pre-emulsified with soy protein isolate. The 15% and 20% substitution were also reached by adding encapsulated flaxseed oil and encapsulated fish oil and by adding flaxseed oil, pre-emulsified with sodium caseinate, respectively. The products were sliced, packaged in an oxygen-enriched atmosphere and stored in the dark for 12 weeks at 7°C. No differences were detected in moisture, protein and fat content between control and modified sausages, with the exception of the formulation with sodium caseinate. The PUFA/SFA ratio increased from 0.30 in the control to 0.42-0.48 in the sausages with canola oil and to 0.49-0.71 in the sausages with flaxseed oil. The n-6/n-3 ratio decreased from 11.20 in the control to 6.94-5.12 in the sausages with canola oil and to 1.93-1.05 in the sausages with flaxseed oil. The addition of canola oil and encapsulated flaxseed oil resulted in a comparable shelf life as the control in terms of lipid oxidation. In the samples with addition of pre-emulsified flaxseed oil, especially with sodium caseinate, lipid oxidation clearly increased during storage. Physical and sensory analysis showed that the sausages with encapsulated fish oil and flaxseed oil resembled the control most.

C22 isomerization in alpha-tomatine-to-esculeoside A conversion during tomato ripening is driven by C27 hydroxylation of triterpenoidal skeleton.

Compositional analysis by liquid chromatography/mass spectrometry of triterpenoid glycosides in different tomato cultivars, ripening stages, and parts of fruits showed that alpha-tomatine was generally most abundant in the flesh of the mature green stage, whereas esculeoside A was predominant in that of the red ripe stage. The sum of these glycoalkaloids was more or less constant, suggesting that alpha-tomatine is converted to esculeoside A during ripening. Besides various substitutions, the C22alphaN --> C22betaN isomerization is an important step in this transformation. By quantum chemical calculations it was shown that hydroxylation at C27 of the triterpenoidal skeleton is the driving force behind the isomerization. For the protonated form of the glycoalkaloid (predominant at the pH of tomato tissue), the C22betaN configuration becomes more favorable than that of C22alphaN, through the extra energy provided by the hydrogen bond between the protonated nitrogen and the lone pair of the oxygen of the C27-OH.