Effect of macromolecules and triton X-100 on the triplet of aggregated chlorophyll in aqueous solution

Chlorophyll a (Chla) in aqueous solution (2-6% acetone) is present as mono- and dihydrated aggregated forms which are characterized by specific ground state absorption spectra. The amount of dihydrated form is larger in the presence of macromolecules, such as bovine serum albumin (BSA), lysozime and polyvinyl alcohol (PVA), increasing from BSA to lysozime and PVA. Chla in aqueous acetone with and without macromolecules is characterized by low fluorescence and the absence of triplet-triplet (T-T) absorption. The ratio of dihydrated to monohydrated forms is significantly influenced by triton X-100. For lower triton X-100 concentrations, i.e. smaller than the critical micelle concentration of 0.26 mM (cmc), dihydrated forms are converted into monohydrated in both aqueous acetone and the presence of BSA or lysozime. In the presence of PVA dihydrated forms appeared to be resistant to triton X-100 action. Moreover, for triton X-100 concentrations of 2-3 times higher than cmc the amount of these forms is increased with time. T-T absorption of both mono- and dihydrated Chla aggregates was not detected in the presence of [triton X-100] < cmc. The lack of T-T absorption in aqueous acetone solution as well as in the presence of macromolecules implies that the triplet lifetime of the chlorophyll aggregates is short (tau(T)<10 ns) and/or the quantum yield of intersystem crossing is small (<5 x 10(-3)). The Chla monomers start to be formed as solubilized in the micelle for [triton X-100] larger than cmc, showing substantial fluorescence and T-T absorption. (C) 2003 Elsevier B.V. All rights reserved.