Alessandra Maria Premoli

Redox activity of caffeic acid towards iron(III) complexed in a polygalacturonate network

The transfer of several metal ions from the soil to the plant absorbing cells is mediated principally by organic molecules of low molecular weight with complexing and reducing activity, among which caffeic acid (CAF) is particularly important. Here we report the results of a survey which deals with the oxidation of CAF by the Fe(III) ions bound to a polygalacturonate network (Fe(III)-PGA network). The interaction between Fe(III) and CAF was studied by using Fe(III)-PGA networks equilibrated in the 2.4-7.0 pH range by means of kinetic and spectroscopic methods. The reducing power was found to depend on the nature of the Fe(III)-PGA network complexes: when the ferric ion was complexed only by the PGA carboxylic groups, a high redox activity was observed, whereas the Fe(III) reduction was found to be lower when a hydroxylic group was inserted in the Fe(III) coordination sphere. The iron complexed in the network was protected from hydrolysis reactions, as shown by the high pH values at which its reduction occurred. Two different fractions of Fe(II) produced were identified, one diffusible and another exchangeable with CaCl2 6.0 mM. The existence of the exchangeable form was attributed to the electrostatic interaction of the Fe(II) ions with the carboxylate groups of the fibrils and with the degradation products of CAF. The arrangement of the fibrils was altered following the substitution of Ca(II) by Fe(III) ions and was restored following the reduction of Fe (III) by CAF.

Zinc(II) adsorption on aluminium hydroxide

Abstract The adsorption of zinc(II) on aluminium hydroxide from ZnSO4 or ZnCl2 solutions in the presence of anions such as chloride, perchlorate or sulphate has been investigated. The results substantiate that the adsorption process depends on several interactive processes occurring in solution (e.g., zinc speciation) and at the oxide—solution interface (specific anion binding). It is suggested that chloride promotes the sorption of chloro-complexes, sulphate enhances the cationic adsorption by making the surface potential more negative, and perchlorate behaves as an indifferent anion. Specific adsorption of cationic species promotes the binding of adsorbing anions.

Influence of organic acids exuded by plants on the interaction of copper with the polysaccharidic components of the root mucilages

Abstract A model of the soil-root interface defined by a network of Ca-polygalacturonate was employed to draw information about the interactions between copper and the polysaccharidic components of the root mucilages. The absorption kinetics show that the matrix has a high affinity and selectivity towards copper and that two carboxylate groups coordinate one metal ion. The complexing activity of the polysaccharidic matrix towards copper was also investigated in the presence of citric, malic, pyruvic, and d -galacturonic acids. The results show that the capacity of the matrix to complex copper is related to the organic acid used, which can be explained on the basis of both the stability constants and concentration of the complexes in solution. The ability of these acids to mobilize copper from the polysaccharidic matrix was also investigated.

Role of Uronic Acid Polymers on the Availability of Iron to Plants

Abstract The interaction between polygalacturonic acid and Fe(III) was studied in the presence and in the absence of pyruvic, malic, and citric acids. Kinetical data and FT‐IR analyses show that the polysaccharidic matrix acts as an accumulator of Fe(III) and that the metal ion interacts electrostatically with both the carboxylic and other functional groups of the polysaccharidic matrix. Copper(II) ions, which have a high affinity towards the carboxylic groups of the polysaccharide, do not influence markedly the Fe(III) absorption indicating that the carboxylic groups are not determining in the Fe(III) accumulation process. Furthermore, the results suggest that iron inside the fibrils is under an hydrolyzed form or as Fe(III) hydroxy polymer. In the presence of malic and citric acids the amount of Fe(III) accumulated at pH 4.7 and 6.0 is markedly lower than that found in the presence of pyruvic acid what was attributed to the higher affinity of citric and malic acid towards the metal ion.

Oxidation of caffeic acid by Fe(III) trapped in a Ca-polygalacturonate network.

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.

Accumulation and mobilization of arsenate by Fe(III) polyions trapped in a Ca-polygalacturonate network.

The role of Fe(III) stored at the soil-root interface in the accumulation of arsenate and the influence of citric acid on the As(V) mobility were investigated by using Ca-polygalacturonate networks (PGA). The results indicate that in the 2.5-6.2 pH range Fe(III) interacts with As(V) leading to the sorption of As(V) on Fe(III) precipitates or Fe-As coprecipitates. The FT-IR analysis of these precipitates evidenced that the interaction produces Fe(III)-As(V) inner-sphere complexes with either monodentate or bidentate binuclear attachment of As(V) depending on pH. In the 3.0-6.0 pH range, As(V) diffuses freely through the polysaccharidic matrix that was found to exert a negligible reducing action towards As(V). At pH 6.0 citric acid is able to mobilize arsenate from the As-Fe-PGA network through the complexation of the Fe(III) polyions that leads to the release of As(V).

Manganese (II)-aluminium hydroxide interaction: An ESR study

Abstract The ESR spectra of air-dried and fully-hydrated gels of aluminium hydroxide exchanged with Mn(II) are described. The results substantiate the presence of two adsorbed species: (i) the ‘free’ species which consists of an hydrated cation retaining almost unperturbed mobility compared with that of [Mn(H 2 O) 6 ] 2+ in dilute aqueous solution; and (ii) the ‘bound’ species which consists of an hydrated cation which interacts directly with the surface sites and is subject to motional restriction and/or geometrical distortion. Specifically adsorbed sulphate favours the formation of the ‘bound’ species.

Interaction of Oxidation Products from Caffeic Acid with Fe(III) and Fe(II)

Abstract Phenolic substances in the soil–plant system can be oxidized by metal ions, inorganic components, molecular oxygen as well as by phenoloxidases, giving rise to the formation of products of low or high molecular weight. Interactions of these products with iron, in both reduced and oxidized form, can affect the iron mobility in soil and rhizosphere, and thus its availability to plants. Here we report the results of a study on the complexing and reducing activity of the oxidation products from caffeic acid (CAF), obtained via electrochemical means, towards Fe(III) and Fe(II) in aqueous solution in the 3.0–6.0 pH range. The HPLC analysis of the filtered solutions after the CAF oxidation showed the formation of two main groups of products: (i) CAF oligomers formed through radicalic reactions which do not involve the double bond of the CAF lateral chain and (ii) products where this bond is involved. These oxidation products (COP) were found to interact with both Fe(III) and Fe(II) with formation of soluble and insoluble Fe(III)‐, and Fe(II)‐COP complexes. The COP were found to be able to reduce Fe(III) to Fe(II) mainly at pH < 4.0. A low redox activity was observed at pH ≥ 4.5 due to Fe(III) hydrolysis reactions as well as to the decrease in the redox potential of the Fe(III)/Fe(II) couple. Formation of hydroxy Fe(III)‐COP polymers occurs at pH > 3.5.

Role of the caffeic acid oxidation products on the iron mobilization at the soil-root interface

Previous results show that the reduction of Fe(III) by caffeiic acid (CAF) is strongly influenced by the pH of the reaction medium (DEIANA et al., 1995). In particular, it has been found that al pH > 3.8 the reducing activity of CAF towards the Fe(III) ions in solution is low, but it increases when Fe(III) is complexed as Fe(III)-polygalacturonate. The mobilization of the Fe(II) ions, which form upon the Fe(III) reduction, has been shown to depend mainly on the nature of the Fe(III)-polygalacturonate complexes (DEIANA et al., 1994a). In particular, it bas been observed a high redox activity of CAF towards Fe(III) when the metal ion is coordinated by the carboxilic groups of the macromolecule. The Fe(III) reduction has been found to decrease when an oxydrilic group was inserted in the Fe(III) coordination sphere. The Fe(II) produced partly diffuses into the external solution and partly is still strongly held by the polysaccharidic matrix. The oxidation of CAF by Fe(III) gives rise to the formation of products (OP) with different polymerization degree, some of which are similar to those found in natural systems (DEIANA et al., 1994b). In order to determine the role of these products in the Fe(III) reduction as well as in the mobilization of the Fe(II) produced it was set up an electrochemical method to synthetize these products (DEIANA et al., 1994b). Here are reported some results about the interaction which establish between the CAF oxidation products and iron in both oxidized and reduced form.

Influence of pH and of several organic acids on the interaction between esculetine and iron(III).

The availability of iron to plants is influenced by organic molecules of low molecular weight with complexing or reducing capacity such as organic acids and phenolic acids and their derivates. To provide information about the interactions between Fe(III) and esculetine (ESC) and the influence of organic acids on these interactions, the redox activity of ESC at different pH values in aqueous solution was investigated in the presence and in the absence of citric, malic, oxalic and pyruvic acid on systems with different Fe(III)/ESC molar ratios. At pH oxalic >malic >>pyruvic acid.