Photoelectric effects in chlorophyll membranes

Abstract Photoinduced potentials and currents and photo-electroosmotic velocities were measured across cellulose acetate membranes impregnated with chlorophyll pigments. Chlorophyll was extracted by both solvent extraction, Chl s , and column chromatography, Chl. Photoelectric effects in membranes prepared with the following pigments were investigated: (i) Chl s -a + β-carotene, (ii) Chl s -b + xanthophyll, (iii) Chl s -a, (iv) Chl s -b, (v) β-carotene, (vi) xanthophyll, (vii) Chl s -a + anthraquinone, (viii) Chl s -b + anthraquinone, (ix) Chl-a, (x) Chl-b, (xi) Chl-a + anthraquinone, (xii) Chl-b + anthraquinone, (xiii) Chl-a + benzoquinone, and (xiv) Chl-b + benzoquinone. β-Carotene, xanthophyll, Chl-a and Chl-b obrained by chromatographic separation do not show a photoinduced potential or current. However, these effects are observed when “pure” (doubly chromatographed) Chl-a or Chl-b are mixed with anthraquinone or benzoquinone. These effects are observed in systems (i), (ii), (iii), (iv), (vii) and (viii) involving Ch s . Although photoinduced potentials and photoinduced currents are not observed in Chl-a or Chl-b membranes, photoelectroosmosis is still observed. p]Both photoinduced potentials and currents are found to depend on pH. When the pH is changed appropriately, Chl s -a acts as photocathode while Chl s -b becomes a photoanode. Photocurrents are considerably enhanced when the pH is lowered. The change of photopotential with temperature is found to be insignificant. Photoelectroosmosis is always found to be directed towards the dark side, regardless of the polarity of the electrodes. A model based on the role of plastiquinone has been proposed to explain these phenomena, which have excellent reproducibility. The model predicts that ΔpH = (pH) d — (PH) 1 (where (pH) d and (pH) 1 denote the pH on the dark and illuminated side of the membrane respectively) would be positive when the pH of the bathing solution is higher than approximately 7, while it would be negative for lower pH. This behaviour is observed in the case of mixture of pure Chl-a + anthraquinone and pure Chl-b + benzoquinone. The model also predicts photoelectroosmosis irrespective of the presence of plastiquinone, in agreement with experimental observation.