Antenna complexes, energy transfer

The sensitisation process associated with producing lanthanide luminescence consists of a number of steps, including excitation of the antenna and energy transfer to the lanthanide. The details of this process and the considerations required in designing complexes working on this principle are discussed in the following sections. 

The photon energy harvested by the antenna complexes is transferred to the RC with almost 100% efficiency by energy migration between the Chi... 

TRANSITION METAL SUPRAMOLECULAR COMPLEXES - ENERGY TRANSFER IN ARTIFICIAL ANTENNAS... 

The analysis of carotenoid identity, conformation, and binding in vivo should allow further progress to be made in understanding of the functions of these pigments in the photosynthetic machinery. One of the obvious steps toward improvement could be the use of continuously tuneable laser systems in order to obtain more detailed resonance Raman excitation profiles (Sashima et al 2000). This technique will be suitable for the investigation of in vivo systems with more complex carotenoid composition. In addition, this method may be applied for the determination of the energy of forbidden Sj or 2 Ag transition. This is an important parameter, since it allows an assessment of the energy transfer relationship between the carotenoids and chlorophylls within the antenna complex. 

Leegwater, J. A. (1996). Coherent versus incoherent energy transfer and trapping in photosynthetic antenna complexes. J. Phys. Chem. 100, 14403-9. 

Figure 10.16 Solar energy transfer from accessory pigments to the reaction centre, (a) The photon absorption by a component of the antenna complex transfers to a reaction centre chlorophyll, or, less frequently, is reemitted as fluorescence, (b) The electron ends up on the reaction centre chlorophyll because its lowest excited state has a lower energy than that of the other antenna pigment molecules. (From Voet and Voet, 2004. Reproduced with permission from John Wiley Sons., Inc.)...

We have seen that, in photosynthetic bacteria, visible light is harvested by the antenna complexes, from which the collected energy is funnelled into the special pair in the reaction centre. A series of electron-transfer steps occurs, producing a charge-separated state across the photosynthetic membrane with a quantum efficiency approaching 100%. The nano-sized structure of this solar energy-conversion system has led researchers over the past two decades to try to imitate the effects that occur in nature. 

An important measure of the luminescence is the quantum yield. In effect, this is the probability that a photon will be emitted by the lanthanide given that one photon has been absorbed by the antenna ligand. Since measurement of absolute quantum yields is particularly difficult, the overall quantum yield ( ) is normally measured with reference to certain standards (26) these are routinely [Ru(bpy)3]2+ in water or SulfoRhodamine 101 in methanol for Eu3 +, and quinoline sulfate in 0.1 M HC1 or fluorescein in 1 N NaOH for Tb3+ (27,28). A method has been developed that measures energy transfer from the lanthanide complex to an acceptor of known quantum yield (28). 

The study of artificial photosynthesis has been the subject of ongoing attention for many years now due to the need for sustainable energy resources. In natural photosynthesis a lightharvesting antenna system with a large optical cross-section (for example the LH2 complex) absorbs a photon that is funneled by energy transfer (ET) to the reaction centre [1-3]. Excellent candidates to mimic the natural antenna system are molecules that efficiently absorb light and are able to transfer the captured energy to other parts of the molecule. Molecules based on Zn and free-base porphyrins are examples of compounds that can be used as models for the LID complex [4]. 

Photosynthetic membranes also contain pigment-protein complexes that serve as antennas. When the antenna absorbs a photon, energy hops rapidly from complex to complex by resonance energy transfer until it is trapped in a reaction center. 

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