Abstract— We determined the polarized and isotropic visible/UV absorption spectra of chlorophyll a (Chi a) and pheophytin a (Pheo a) oriented in the lamellar phase of glycerylmonooctanoate/H2O. Resolution into mutually perpendicular X‐ and Y‐polarized absorption spectra of the pigments was achieved assuming that the transition moments of Chi a and Pheo a are located in the plane of the chromophores. The polarized spectra were deconvoluted into harmonic progressions and the resultant assignment of band positions in the long‐wavelength region was found to correlate well with independent spectral measurements, such as the polarisation of fluorescence. However, the correlation of the experimentally determined transitions with the results of theoretical calculations is not straightforward. The overall conclusions are of fundamental interest in the determination of orientations of the tetrapyrrole macrocycle in lipid lamellae and pigment‐protein structures of photosynthetic membranes.

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Electron transport through photosystem II, measured as oxygen evolution (OE), was investigated in isolated thylakoid membranes treated with beta-cyclodextrin (beta-CD, a cyclic oligosaccharide constituted of seven alpha-d-glucose residues linked by alpha-1,4 glycosidic bonds) and irradiated with white light of variable intensity. First, we found that the light-response curves of oxygen evolution are well fitted with a hyperbolic function, the shape of which is not affected by the beta-CD concentration. Second, we showed that under conditions of irradiation with white light of saturating intensity ( approximately 5000 mumol of photons/m(2).s) beta-CD enhances the oxygen evolution in the thylakoid membranes according to a sigmoid function displaying a sharp inflection point, or transition. Unexpectedely, this beta-CD effect is not observed at irradiances of less than approximately 300 mumol of photons/m(2).s. We attempted a theoretical analysis of the combined effect of irradiance and beta-CD concentration on oxygen evolution (OE(th)). For this purpose, the effect of irradiance (I) was modeled with a hyperbola (i) and the beta-CD concentration (C) contribution with a Hill equation, that is, a sigmoid function (ii). The mathematical simulations generated the following general expressions: (i) OE(th) = [OE(max)(0) G(1)(C)]I/[L(1/2)(0) G(2)(C) + I] and (ii) G(i)()(C) = 1 + p[C(n)()/(K(1/2)(n)() + C(n)())], where OE(max)(0) is the OE maximum (OE(max)) in the absence of beta-CD, L(1/2)(0) is the photon flux density giving OE(max)/2 in the absence of beta-CD, G(1)(C) or G(2)(C) is obtained from G(i)()(C) where i is 1 or 2, n is the Hill coefficient, p is a parameter to account for the beta-CD-mediated maximum OE increase, and K(1/2) is the beta-CD concentration giving half-maximal OE activity. The results of the calculations yielded the expression (iii) OE(th) = 151[1 + 3.3C(4.8)/(13.1(4.8) + C(4.8))]I/{97.5[1 + 5.2C(7.8)/(14.8(7.8) + C(7.8))] + I} which agrees well with the experimental data for a broad range of I and C. Note that, for C = 0, eq iii reverts to the light-response curve of oxygen evolution in the absence of beta-CD. We conclude that eq iii is a good approximation of the combined effect of irradiance and beta-CD concentration, meaning that the model has a significant value for predicting the outcome of associated photochemical and biochemical reactions.

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