Dataset Information

Ru-protein-Co biohybrids designed for solar hydrogen production: understanding electron transfer pathways related to photocatalytic function.

ABSTRACT: A series of Ru-protein-Co biohybrids have been prepared using the electron transfer proteins ferredoxin (Fd) and flavodoxin (Fld) as scaffolds for photocatalytic hydrogen production. The light-generated charge separation within these hybrids has been monitored by transient optical and electron paramagnetic resonance spectroscopies. Two distinct electron transfer pathways are observed. The Ru-Fd-Co biohybrid produces up to 650 turnovers of H2 utilizing an oxidative quenching mechanism for Ru(ii)* and a sequential electron transfer pathway via the native [2Fe-2S] cluster to generate a Ru(iii)-Fd-Co(i) charge separated state that lasts for ?6 ms. In contrast, a direct electron transfer pathway occurs for the Ru-ApoFld-Co biohybrid, which lacks an internal electron relay, generating Ru(i)-ApoFld-Co(i) charge separated state that persists for ?800 ?s and produces 85 turnovers of H2 by a reductive quenching mechanism for Ru(ii)*. This work demonstrates the utility of protein architectures for linking donor and catalytic function via direct or sequential electron transfer pathways to enable stabilized charge separation which facilitates photocatalysis for solar fuel production.

SUBMITTER: Soltau SR

PROVIDER: S-EPMC5355951 | biostudies-literature | 2016 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Ru-protein-Co biohybrids designed for solar hydrogen production: understanding electron transfer pathways related to photocatalytic function.

Soltau Sarah R SR Dahlberg Peter D PD Niklas Jens J Poluektov Oleg G OG Mulfort Karen L KL Utschig Lisa M LM

Chemical science 20160816 12

A series of Ru-protein-Co biohybrids have been prepared using the electron transfer proteins ferredoxin (Fd) and flavodoxin (Fld) as scaffolds for photocatalytic hydrogen production. The light-generated charge separation within these hybrids has been monitored by transient optical and electron paramagnetic resonance spectroscopies. Two distinct electron transfer pathways are observed. The Ru-Fd-Co biohybrid produces up to 650 turnovers of H<sub>2</sub> utilizing an oxidative quenching mechanism ...[more]

PMID: 28451142

Similar Datasets

Project description:Achieving global sustainability will require balancing encroaching climate changes while maintaining existing quality of life. Using sunlight to purify wastewater while simultaneously generating usable fuels is an opportunity to approach both targets in a cost-efficient manner. In addition, converting biomass products to usable polymers is a sustainable approach for potentially replacing polystyrene or other petroleum derived polymers. Phenols from medical, manufacturing, and agricultural waste are commonly found in many water sources, and they are known to foul common reverse osmosis membranes. Here, we show oxidative polymerization of guaiacol, an aromatic compound derived from biomass, with concurrent hydrogen gas generation by using platinum-seeded cadmium sulfide nanorods (Pt@CdS) as photocatalysts. Rather than forming short oligomers as typically made by enzymes such as laccase and peroxidase, the resulting polymers show higher molecular weights that can more easily flocculate out of water. By comparing guaiacol conversion to molecular weight and dispersity, the guaiacol was found to polymerize via a chain-growth process. We also show that Pt@CdS can polymerize other phenols as well by testing the monomers phenol, 2,6-dihydroxybenzoic acid, gallic acid, and vanillin. Lastly, because the aqueous solubility of these aromatic polymers decreases dramatically with molecular weight, polymerization reactions were also tested in biphasic solutions to determine if chain growth could propagate in the oil phase. We show that the Pt@CdS nanoparticles can form stable Pickering emulsions in various biphasic combinations, and that both H2 formation and polymer molecular weight correlated with the partition coefficient of guaiacol into the oil phase as well as the solubility of the growing polymer chains. These combined studies demonstrate the possibility of using nanoscale photocatalysts to oxidatively polymerize phenolic substrates via a chain-growth mechanism, thereby providing a path for pretreating water by flocculating out contaminants with concurrent generation of hydrogen.

Dataset Information

Ru-protein-Co biohybrids designed for solar hydrogen production: understanding electron transfer pathways related to photocatalytic function.

Publications

Ru-protein-Co biohybrids designed for solar hydrogen production: understanding electron transfer pathways related to photocatalytic function.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets