pectins and caffeic-acid

In the root apoplasm, V(V) and V(IV) toxicity can be alleviated through redox and complexation reactions involving phenolic substances and the polyuronic components. In such context we report the role of polygalacturonic acid (PGA) on the reducing activity of caffeic acid (CAF) towards V(V). The redox reaction was particularly effective at pH 2.8 leading to the formation of oxidation products with redox activity towards V(V). An o-quinone was identified as the first product of the reaction which is further involved in the formation of CAF dimers. At pH ≥ 3.6 the redox activity decreased and a yield in V(IV) equal to 38, 31, 21 and 14% was found at pH 3.6, 4.0. 5.0 and 6.0 respectively compared with that obtained at pH 2.8. The redox reaction was faster in the presence of PGA and a higher yield of V(IV) was found in the 4.0-6.0 pH range with respect to the CAF-V(V) binary system. The higher efficiency of the redox reaction in the presence of PGA was related with the ability of PGA to bind V(IV). The biological significance of the redox reaction between CAF and V(V), as well as the role of PGA in such reaction, was established "in vivo" using triticale plants. Results showed that PGA reduced significantly the phytotoxic effects of the V(V)-CAF system.

Topics: Caffeic Acids; Environmental Pollutants; Environmental Pollution; Inactivation, Metabolic; Oxidation-Reduction; Pectins; Plant Roots; Plants; Vanadates

With the aim to verify if Fe(III) ions accumulated in a network of Ca-polygalacturonate (PGA) may promote the oxidation of caffeic acid (CAF) the interaction at pH 5.0 between CAF and Fe(III) ions trapped in a PGA was studied. The sorption kinetics evidenced a great affinity of CAF towards the Fe-PGA matrix. Chromatographic tests showed that the interaction leads to the formation of products which can be considered as CAF oligomers characterized by FT-IR spectra similar to those of natural humic acids. Tests carried out under nitrogen suggest that at pH 5.0 oxygen does not affect the nature of these oxidation products. Oxygen was hypothesized to exert a direct action on the redox process by oxidizing the Fe(II) ions, produced by oxidation of CAF, to Fe(III) thus regenerating oxidizing sites. A possible mechanism of formation of the polymers was proposed that implies that the CAF oxidation leads to highly reactive species such as semiquinones which give rise, by an oxidative coupling reaction, to the formation of oligomers that can aggregate through secondary bonds to produce more complex structures as those that characterize humic acids.

Topics: Benzoquinones; Caffeic Acids; Cations; Humic Substances; Hydrogen-Ion Concentration; Iron; Oxidation-Reduction; Oxygen; Pectins