Polarography of conjugated unsaturated lipids

Abstract

Conjugated fat-soluble vitamins, methylenic interrupted and conjugated fatty acids were polarographically investigated in both basic and neutral solvents. The half-wave potentials of all-trans-retinol, 13-cis-retinol, all-trans-retinyl acetate, all-trans-retinal, and Vitamin D(2) and D(3) were related to the number of double bonds in conjugation and their geometrical configuration. A minimum of three double bonds in conjugation and their geometrical configuration. A minimum of three double bonds in conjugation was required before reduction took place at the cathode, and as the number of conjugated bonds increased in the lipid compounds, the initial reduction wave took place at a lower half-wave potential.Investigation of conjugated double bonds in triglycerides and in alkali-isomerized linolenic and arachidonic acids gave reduction waves the half-wave potentials of which were related to the number of double bonds in conjugation. In both basic and neutral solvents there was a minimum of three double bonds in conjugation necessary to obtain a reduction wave at the dropping mercury electrode. Ultraviolet absorption curves of the prolonged reduction of polyunsaturated conjugated fatty acids indicate a step-wise reduction of each end of the polyunsaturated conjugated double bonds.In neutral solvent the log of the conjugated double bonds versus the half-wave potential (versus mercury pool anode) gave a linear equation, E(1)=2.98-1.6 log C. A proposed mechanism for the step-wise reduction of conjugated lipids is presented and discussed.