Virus-Templated Assembly of Porphyrins into Light-Harvesting Nanoantennae

Abstract

Biological molecules can be used as versatile templates for assembling nanoscale materials because of their unique structures and chemical diversities. Supramolecular organization of molecular pigments, as is found in the natural light-harvesting antenna, has drawn attention for its potential applications to sensors, photocatalytic systems, and photonic devices. Here we show the arrangement of molecular pigments into a one-dimensional light-harvesting antenna using M13 viruses as scaffolds. Chemical grafting of zinc porphyrins to M13 viruses induces distinctive spectroscopic changes, including fluorescence quenching, the extensive band broadening and small red shift of their absorption spectrum, and the shortened lifetime of the excited states. Based on these optical signatures we suggest a hypothetical model to explain the energy transfer occurring in the supramolecular porphyrin structures templated with the virus. We expect that further genetic engineering of M13 viruses can allow us to coassemble other functional materials (e.g., catalysts and electron transfer mediators) with pigments, implying potential applications to photochemical devices.

Geometrical effects on energy transfer in disordered open quantum systems

“…However, if such regime is practically inaccessible, here we found alternative scenarios for potential optimal material design beyond Goldilocks regime where certain configurations could still have high energy efficiencies, e.g., due to constructive quantum interference effects, but they become very sensitive to defects or environmental fluctuations. These model studies could be useful for design of structured molecular aggregates such as self-assembled dyes on tubular J-aggregates 46,47 and virusbased templates aggregates, 37,38,48,49 with potential applications to photovoltaic devices, photosensing, and biological sensing.…”

Exciton Level Structure and Dynamics in Tubular Porphyrin Aggregates

“…11,[16][17] Tubular aggregates formed by self-assembly of dye molecules represent one of the most promising constructs for biomimetic photosynthetic antenna systems. 5,7,[18][19][20] A prominent example of tubular molecular aggregates is derived from meso-tetra(4-sulfonatophenyl) porphyrin (TPPS4) and provides a biomimetic analogue of the chlorosomes of green sulfur bacteria. 9,[21][22][23][24] The structure of TPPS4 tubular aggregates has been characterized by small angle X-ray scattering, atomic force microscopy (AFM), and cryo-electron microscopy.…”

Simple Peptide‐Tuned Self‐Assembly of Photosensitizers towards Anticancer Photodynamic Therapy

“…Scanning electron microscopy (SEM) images of the separated precipitate showed the presence of uniform spherical structures with average diameters of about 100 nm for Fmoc-l-Lys/Ce6 nanoparticles (FCNPs;F igure 1a), and about 200 nm for CDP/Ce6 nanoparticles (CCNPs;F igure 1c)i nt he given Theco-assembly of Ce6 with Fmoc-l-Lys or CDP results in ac onsiderably broader and red-shifted Soret band (Figure 2a), as expected for aggregates of different size or structure. [12] TheF moc groups of Fmoc-l-Lys and the aromatic residues in CDP can interact with the pyrrole groups of Ce6 by hydrophobic and p-p interactions.I n acontrol test, hydrophilic dilysine (KK) was mixed with Ce6, while no NPs were formed ( Figure S4). This indicates that hydrophobic and p-p interactions between Fmoc-l-Lys or CDP and Ce6 contribute to the coassembly.T he turbidity of the suspension of the NPs decreases in an environment of high ionic strength (Figure 2b), indicating the disassembly of NPs.T his suggests the existence of electrostatic forces in the coassembly process.T he fluorescence of assembled NPs (such as FCNPs) was dramatically suppressed compared to monomeric Ce6 ( Figure S5).…”