In the Ni-substituted chlorophylls, an ultrafast (<60 fs) deactivation channel is created, which is not present in Ni-porphyrins. This observation prompted us to investigate in detail the mechanism of excitation-to-heat conversion in Ni-substituted chlorophylls, experimentally, using time-resolved laser-induced optoacoustic spectroscopy, and theoretically, using group theory approach. The Ni-substituted chlorophylls show exceptional photostability and the optoacoustic measurements confirm the prompt and very efficient (100%) excitation-into-heat conversion in these complexes. Considering their excellent spectral properties and the loss-free excitation-into-heat conversion they are likely to become a new class of versatile photocalorimetric references. The curious features of the Ni-substituted chlorophylls originate from the symmetry of a ligand field created in the central cavity. The central N-Ni(2+) bonds, formed via the donation of two electrons from each of the sp(2) orbitals of two central nitrogens to an empty [Formula: see text] hybrid centered on Ni(2+), have a considerable covalent character. The extreme rate of excited state relaxation is then not due to a ladder of the metal centered d-states, often invoked in metalloporphyrins, but seems to result from a peculiar topology of the potential energy surface (a saddle-shaped crossing) due to the covalent character of the N-Ni(2+) bonds. This is confirmed by a strong 0→0 character of electronic transitions in these complexes indicating a similarity of their equilibrium geometries in the ground (S(0)) and the excited states (both Q(X) and Q(Y)). The excitation energy is very efficiently converted into molecular vibrations and dissipated as heat, involving the central Ni(2+). These Ni-substituted pigments pose a fine exemplification of symmetry control over properties of excited states of transition metal complexes.

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The toxic effect of six heavy metals on cyanobacteria Synechocystis aquatilis was studied by absorption, fluorescence, flow cytometry, and photothermal measurements. This study indicates that at the concentration used, the cyanobacteria are more sensitive to silver, copper, and mercury than to cadmium, lead, and zinc metals. Disregarding the decrease in the yields of the related radiative processes caused by photochemical processes and/or damage to phycobilisomes, no changes were detected in the efficiency of thermal deactivation processes within a few microseconds, which can indicate the lack of disturbances in the photosynthetic light reaction and the lack of damage to the photosystem caused by the heavy metal ions in the concentrations used. The results demonstrate that the relative values of fluorescence yield as well as promptly generated heat calculated for the metal-affected and unaffected (reference) bacteria are sensitive indicators of environmental pollution with heavy metal ions, whereas the complementary methods proposed could be used as a noninvasive and fast procedure for in vivo assessment of their toxicity.

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To achieve better understanding of anticancer photosensitizing efficiency and cellular membrane location ability, a study of hematoporphyrin and phospholipids in a dye and in a mixture of a dye and lipids in volumetric and 2D systems was performed. By means of steady-state absorption, fluorescence, and time-resolved optoacoustic spectroscopy, the fluorescence quantum yield, the fraction of absorbed energy converted into heat on a subnanosecond timescale, the efficiency of the dye's triplet-state population, and singlet oxygen generation characteristics of the dye were determined in chosen organic solvents. On the basis of the isotherms of hematoporphyrin and its mixture with phospholipid in Langmuir monolayers, the excess area, excess Gibbs energy, and compression modulus were estimated and the molecular interactions in the model systems investigated were discussed.

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