Red chlorophyll excitation dynamics in Arthrospira platensis photosystem I trimeric complexes as studied by femtosecond transient absorption spectroscopy.

Femtosecond absorption spectroscopy was applied to study for the first time excitation dynamics in isolated photosystem I trimers from Arthrospira platensis, which display extremely long-wavelength absorption peaks. Pump-probe spectra observed at 77K in the timescale of dozens of picoseconds upon 70-fs excitation revealed two maxima near 710 and 730 nm, which correspond to red chlorophyll forms. Bleaching at 680 nm developed in ∼ 200 fs, whereas the bleaching kinetics at 710 and 730 nm exhibited two components with time constants of 1 and 5.5 ps. Comparison of the kinetics of bleaching development at 710 nm and 730 nm with that of bleaching decay at 680 nm indicated that both long-wavelength forms of trimers are populated mainly via direct energy transfer from bulk chlorophyll.

Long-wavelength limit of photochemical energy conversion in Photosystem I.

In Photosystem I (PS I) long-wavelength chlorophylls (LWC) of the core antenna are known to extend the spectral region up to 750 nm for absorbance of light that drives photochemistry. Here we present clear evidence that even far-red light with wavelengths beyond 800 nm, clearly outside the LWC absorption bands, can still induce photochemical charge separation in PS I throughout the full temperature range from 295 to 5 K. At room temperature, the photoaccumulation of P700(+•) was followed by the absorbance increase at 826 nm. At low temperatures (T < 100 K), the formation of P700(+•)FA/B(-•) was monitored by the characteristic EPR signals of P700(+•) and FA/B(-•) and by the characteristic light-minus-dark absorbance difference spectrum in the QY region. P700 oxidation was observed upon selective excitation at 754, 785, and 808 nm, using monomeric and trimeric PS I core complexes of Thermosynechococcus elongatus and Arthrospira platensis, which differ in the amount of LWC. The results show that the LWC cannot be responsible for the long-wavelength excitation-induced charge separation at low temperatures, where thermal uphill energy transfer is frozen out. Direct energy conversion of the excitation energy from the LWC to the primary radical pair, e.g., via a superexchange mechanism, is excluded, because no dependence on the content of LWC was observed. Therefore, it is concluded that electron transfer through PS I is induced by direct excitation of a proposed charge transfer (CT) state in the reaction center. A direct signature of this CT state is seen in absorbance spectra of concentrated PS I samples, which reveal a weak and featureless absorbance band extending beyond 800 nm, in addition to the well-known bands of LWC (C708, C719 and C740) in the range between 700 and 750 nm. The present findings suggest that nature can exploit CT states for extending the long wavelength limit in PSI even beyond that of LWC. Similar mechanisms may work in other photosynthetic systems and in chemical systems capable of photoinduced electron transfer processes in general.

Manipulating the excitation transfer in Photosystem I using a Fabry-Perot metal resonator with optical subwavelength dimensions.

We demonstrate controlled modification of the fluorescence and energy transfer properties of Photosystem I (PSI) - one of the most important light harvesting systems - by using a newly developed approach to produce optical subwavelength microcavities for cryogenic temperature issues. The experiments were carried out on PSI from the cyanobacterium Arthrospira platensis as it shows a broad and structured fluorescence emission. By changing the distance between the cavity forming mirrors, the electromagnetic field mode structure around PSI is varied affecting the emission and energy transfer properties, which allows us to selectively enhance signals of resonant emitters and suppress off-resonant emission. By comparing the experimental data with simulations, we are able to show how excitation transfer within PSI is affected by the microcavity. The ability to control the energy transfer within such efficient energy converters as photosynthetic proteins can establish the opportunity for enhancing the efficiencies of bio-solar applications. The defined control of the resonance conditions by microcavities makes them a preferable tool to study the effects of additional electromagnetic modes on the energy transfer in any coupled multi-chromophore system. The resonator geometry excludes the direct contact of the proteins with any surface. Possible quenching or denaturation of the complexes close to metal surfaces is still an insuperable obstacle for studies with proteins and nanostructures, which can be avoided by resonators.