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The inhibitory effect of Al3+on photosystem II (PSII) electron transport was investigated using several biophysical and biochemical techniques such as oxygen evolution, chlorophyll fluorescence induction and emission, SDS-polyacrylamide and native green gel electrophoresis, and FTIR spectroscopy. In order to understand the mechanism of its inhibitory action, we have analyzed the interaction of this toxic cation with proteins subunits of PSII submembrane fractions isolated from spinach. Our results show that Al 3+, especially above 3 mM, strongly inhibits oxygen evolution and affects the advancement of the S states of the Mn4O5Ca cluster. This inhibition was due to the release of the extrinsic polypeptides and the disorganization of the Mn4O5Ca cluster associated with the oxygen evolving complex (OEC) of PSII. This fact was accompanied by a significant decline of maximum quantum yield of PSII (Fv/Fm) together with a strong damping of the chlorophyll a fluorescence induction. The energy transfer from light harvesting antenna to reaction centers of PSII was impaired following the alteration of the light harvesting complex of photosystem II (LHCII). The latter result was revealed by the drop of chlorophyll fluorescence emission spectra at low temperature (77 K), increase of F0 and confirmed by the native green gel electrophoresis. FTIR measurements indicated that the interaction of Al 3+ with the intrinsic and extrinsic polypeptides of PSII induces major alterations of the protein secondary structure leading to conformational changes. This was reflected by a major reduction of α-helix with an increase of β-sheet and random coil structures in Al 3+-PSII complexes. These structural changes are closely related with the functional alteration of PSII activity revealed by the inhibition of the electron transport chain of PSII.

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The photo-stability of photosystem I (PSI) is of high importance for the photosynthetic processes. For this reason, we studied the protective action of two biogenic polyamines (PAs) spermine (Spm) and spermidine (Spd) on PSI activity in isolated thylakoid membranes subjected to photoinhibition. Our results show that pre-loading thylakoid membranes with Spm and Spd reduced considerably the inhibition of O2 uptake rates, P700 photooxidation and the accumulation of superoxide anions (O2 −) induced by light stress. Spm seems to be more effective than Spd in preserving PSI photo-stability. The correlation of the extent of PSI protection, photosystem II (PSII) inhibition and O2 − generation with increasing Spm doses revealed that PSI photo-protection is assumed by two mechanisms depending on the PAs concentration. Given their antioxidant character, PAs scavenge directly the O2 − generated in thylakoid membranes at physiological concentration (1 mM). However, for non-physiological concentration, the ability of PAs to protect PSI is due to their inhibitory effect on PSII electron transfer.

In this study, we examined the relevance of polyphenols in the response of sunflower plants to acute Cu and Cd stresses. More specifically, we aimed to correlate spatially and temporally the accumulation of polyphenols with the occurrence of oxidative stress, and to estimate their contribution to the antioxidant capacities. Under our experimental conditions, the presence of Cu and Cd (75 µmol·L–1) in the nutrient solution caused oxidative damage, as detected by the accumulation of malondialdehyde, in roots of Cu-treated plants and in leaves of Cd-treated plants; in the latter, significant inhibition of photosynthesis also occurred. These effects were in agreement with the preferential accumulation of Cu in the roots and the greater translocation of Cd to the shoots. This oxidative damage was associated with a concerted plant response, characterized by stimulation of phenylalanine ammonia-lyase, ascorbate peroxidase, and guaiacol peroxidase activities, and by the accumulation of polyphenols whose concentrations were closely correlated (R2 = 0.95) to the total antioxidant capacity of plants extracts. Globally, the co-occurrence of oxidative damages and polyphenol accumulation, and the correlations among polyphenol concentrations, total antioxidant capacities, and stimulations of the peroxidases support the involvement of polyphenols in protection against oxidative damage generated by Cu and Cd in plants.