Ultrafast laser spectroscopic studies on carotenoids in solution and on those bound to photosynthetic pigment-protein complexes.

Carotenoid excited singlet states, in particular, are typically very short lived. Therefore, time-resolved absorption spectroscopy in the time regime from femtoseconds to sub-milliseconds are required to unravel and understand the complicated relaxation and excitation energy-transfer pathways of carotenoids in solution and in photosynthetic pigment-protein complexes. The focus of this chapter is to explain how to use ultrafast time-resolved absorption spectroscopy in carotenoid research. The importance of a systematic approach to understanding the various carotenoid excited states by using a series of carotenoids with different conjugation lengths and the isomers of carotenoids is also emphasized.

Intramolecular charge-transfer enhances energy transfer efficiency in carotenoid-reconstituted light-harvesting 1 complex of purple photosynthetic bacteria.

In bacterial photosynthesis, the excitation energy transfer (EET) from carotenoids to bacteriochlorophyll a has a significant impact on the overall efficiency of the primary photosynthetic process. This efficiency can be enhanced when the involved carotenoid has intramolecular charge-transfer (ICT) character, as found in light-harvesting systems of marine alga and diatoms. Here, we provide insights into the significance of ICT excited states following the incorporation of a higher plant carotenoid, ß-apo-8'-carotenal, into the carotenoidless light-harvesting 1 (LH1) complex of the purple photosynthetic bacterium Rhodospirillum rubrum strain G9+. ß-apo-8'-carotenal generates the ICT excited state in the reconstituted LH1 complex, achieving an efficiency of EET of up to 79%, which exceeds that found in the wild-type LH1 complex.

Understanding/unravelling carotenoid excited singlet states.

Carotenoids are essential light-harvesting pigments in natural photosynthesis. They absorb in the blue-green region of the solar spectrum and transfer the absorbed energy to (bacterio-)chlorophylls, and thus expand the wavelength range of light that is able to drive photosynthesis. This process is an example of singlet-singlet excitation energy transfer, and carotenoids serve to enhance the overall efficiency of photosynthetic light reactions. The photochemistry and photophysics of carotenoids have often been interpreted by referring to those of simple polyene molecules that do not possess any functional groups. However, this may not always be wise because carotenoids usually have a number of functional groups that induce the variety of photochemical behaviours in them. These differences can also make the interpretation of the singlet excited states of carotenoids very complicated. In this article, we review the properties of the singlet excited states of carotenoids with the aim of producing as coherent a picture as possible of what is currently known and what needs to be learned.

Strategies to enhance the excitation energy-transfer efficiency in a light-harvesting system using the intra-molecular charge transfer character of carotenoids.

Fucoxanthin is a carotenoid that is mainly found in light-harvesting complexes from brown algae and diatoms. Due to the presence of a carbonyl group attached to polyene chains in polar environments, excitation produces an excited intra-molecular charge transfer. This intra-molecular charge transfer state plays a key role in the highly efficient (∼95%) energy-transfer from fucoxanthin to chlorophyll a in the light-harvesting complexes from brown algae. In purple bacterial light-harvesting systems the efficiency of excitation energy-transfer from carotenoids to bacteriochlorophylls depends on the extent of conjugation of the carotenoids. In this study we were successful, for the first time, in incorporating fucoxanthin into a light-harvesting complex 1 from the purple photosynthetic bacterium, Rhodospirillum rubrum G9+ (a carotenoidless strain). Femtosecond pump-probe spectroscopy was applied to this reconstituted light-harvesting complex in order to determine the efficiency of excitation energy-transfer from fucoxanthin to bacteriochlorophyll a when they are bound to the light-harvesting 1 apo-proteins.