Over several billion years, cyanobacteria and plants have evolved highly organized photosynthetic systems to shuttle both electronic and chemical species for the efficient oxidation of water. In a similar manner to reaction centres in natural photosystems, molecular and metal oxide catalysts have been used to photochemically oxidize water. However, the various approaches involving the molecular design of ligands, surface modification and immobilization still have limitations in terms of catalytic efficiency and sustainability. Here, we demonstrate a biologically templated nanostructure for visible light-driven water oxidation that uses a genetically engineered M13 virus scaffold to mediate the co-assembly of zinc porphyrins (photosensitizer) and iridium oxide hydrosol clusters (catalyst). Porous polymer microgels are used as an immobilization matrix to improve the structural durability of the assembled nanostructures and to allow the materials to be recycled. Our results suggest that the biotemplated nanoscale assembly of functional components is a promising route to significantly improved photocatalytic water-splitting systems.

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.

One of the challenges for achieving efficient exciton transport in solar energy conversion systems is precise structural control of the light-harvesting building blocks. Here, we create a tunable material consisting of a connected chromophore network on an ordered biological virus template. Using genetic engineering, we establish a link between the inter-chromophoric distances and emerging transport properties. The combination of spectroscopy measurements and dynamic modelling enables us to elucidate quantum coherent and classical incoherent energy transport at room temperature. Through genetic modifications, we obtain a significant enhancement of exciton diffusion length of about 68% in an intermediate quantum-classical regime.

A highly porous electrode comprised of biologically templated iridium oxide-gold (IrO(2)-Au) hybrid nanowires is introduced for electrochromic applications. A filamentous M13 virus is genetically engineered to display IrO(2)-binding peptides on the viral surface and used as a template for the self-assembly of IrO(2) nanoclusters into a nanowire. The open porous morphology of the prepared nanowire film facilitates ion transport. Subsequently, the redox kinetics of the IrO(2) nanowires seems to be limited by the electric resistance of the nanowire film. To increase the electron mobility in the nanowires, gold nanoparticles are chemically linked to the virus prior to the IrO(2) mineralization, forming a gold nanostring structure along the long axis of the virus. The resulting IrO(2)-Au hybrid nanowires exhibit a switching time of 35 ms for coloration and 25 ms for bleaching with a transmission change of about 30.5% at 425 nm. These values represent almost an order of magnitude faster switching responses than those of an IrO(2) nanowire film having the similar optical contrast. This work shows that genetically engineered viruses can serve as versatile templates to co-assemble multiple functional molecules, enabling control of the electrochemical properties of nanomaterials.

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Early diagnosis increases the treatment success rate for active tuberculosis (ATB) and decreases mortality. MicroRNAs (miRNAs) have been studied as blood-based markers of several infectious diseases. We performed miRNA profiling to identify differentially expressed (DE) miRNAs using whole blood samples from 10 healthy controls (HCs), 15 subjects with latent tuberculosis infection (LTBI), and 12 patients with ATB, and investigated the expression of the top six miRNAs at diagnosis and over the treatment period in addition to performing miRNA-target gene network and gene ontology analyses. miRNA profiling identified 84 DE miRNAs in patients with ATB, including 80 upregulated and four downregulated miRNAs. Receiver operating characteristic curves of the top six miRNAs exhibited excellent distinguishing efficiency with an area under curve (AUC) value > 0.85. Among them, miR-199a-3p and miR-6886-3p can differentiate between ATB and LTBI. Anti-TB treatment restored the levels of miR-199b-3p, miR-199a-3p, miR-16-5p, and miR-374c-5p to HC levels. Furthermore, 108 predicted target genes were related to the regulation of cellular amide metabolism, intrinsic apoptotic signaling, translation, transforming growth factor beta receptor signaling, and cysteine-type endopeptidase activity. The DE miRNAs identified herein are potential biomarkers for diagnosis and therapeutic monitoring in ATB.

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