Fluorescent quantum dots as artificial antennas for enhanced light harvesting and energy transfer to photosynthetic reaction centers.

The development of artificial photosynthetic systems that utilize solar energy is one of the most challenging goals of chemistry and material sciences. The straightforward way to construct an artificial photosynthetic device for practical solar fuel production for the practical use of solar energy is to mimic the structural and functional organization of the natural photosynthetic machinery. In photosynthetic organisms, light is initially absorbed by antenna protein–pigment complexes in which it induces an excited electronic state (exciton), and then excitons (or electron–hole pairs) are transferred by means of F rster resonance energy transfer (FRET) to specialist chlorophyll cofactors in specialized reaction centers (RCs); here, excitons dissociate into their constituent carriers which are used in chemical transformations for the synthesis of high-energy molecules that fuel the organism. An artificial device that mimics this process for solar energy conversion should include, among other components, an efficient light-harvesting antenna capable of transferring the excitation energy to the RC. Based on the principle of photosynthesis, a variety of artificial antenna systems have been developed using supramolecular chemistry in which dendrimers incorporate porphyrins or other organic fluorophores or organometallic complexes. Although efficient excitation-energy transfer was obtained in such systems, the use of organic fluorophores in light-harvesting systems is rather limited because of their narrow spectral windows for light-collecting and lack of photostability. Recently it was suggested that inorganic nanocrystals, which are able to collect light over a wide spectral window, may achieve significantly greater absorption than natural photosystems, thus enhancing and could thus be used to enhance the light-harvesting process. Simultaneously, these nanocrystals may also be very efficient in excitationenergy transfer. This has led us to contemplate the development of hybrid materials in which light energy harvested by the nanocrystals in the optical region may be transferred to the RC in order to enhance the efficiency of the photosynthetic process. The simplest and best understood photosynthetic RC is that found in purple bacteria (Rhodobacter sphaeroides, for example). Although RCs from different photosynthetic organisms vary in their structure and composition, they are always composed of complexes of pigments and proteins, and RC fromRb. sphaeroides is known to be a good model of all the photosynthetic RCs. Here, we demonstrate that photoluminescent quantum dots (QDs) of these selected photoluminescence (PL) wavelengths may be tagged with the RC of Rh. sphaeroides in such a way that FRET from the QD to the RC is realized (Figure 1). A nearly threefold increase in the rate of generation of excitons in the RC is demonstrated, and theoretical estimates predict even stronger enhancements, thus indicating that further optimization is possible. Advances in inorganic synthesis have resulted in the production of monodispersed QDs such as highly photoluminescent CdSe/ZnS core/shell and CdTe nanocrystals. The light absorption by these QDs appears as a quasicontinuous superposition of peaks with extinction coefficients orders of magnitude higher than those of organic molecules. QDs are ultrastable against photobleaching, and the quantum [*] Prof. I. Nabiev CIC NanoGUNE Consolider, 20018 San Sebastian (Spain) and EA n83798, Universit de Reims Champagne-Ardenne 51100 Reims (France) and Ikerbasque, Basque Foundation for Science 48011 Bilbao (Spain) Fax: (+34)943-574-001 E-mail: i.nabiev@nanogune.eu