Light-driven fine chemical production in yeast biohybrids.

Inorganic-biological hybrid systems have potential to be sustainable, efficient, and versatile chemical synthesis platforms by integrating the light-harvesting properties of semiconductors with the synthetic potential of biological cells. We have developed a modular bioinorganic hybrid platform that consists of highly efficient light-harvesting indium phosphide nanoparticles and genetically engineered , a workhorse microorganism in biomanufacturing. The yeast harvests photogenerated electrons from the illuminated nanoparticles and uses them for the cytosolic regeneration of redox cofactors.

Interfacing nature's catalytic machinery with synthetic materials for semi-artificial photosynthesis.

Semi-artificial photosynthetic systems aim to overcome the limitations of natural and artificial photosynthesis while providing an opportunity to investigate their respective functionality. The progress and studies of these hybrid systems is the focus of this forward-looking perspective. In this Review, we discuss how enzymes have been interfaced with synthetic materials and employed for semi-artificial fuel production.

Bacteria photosensitized by intracellular gold nanoclusters for solar fuel production.

The demand for renewable and sustainable fuel has prompted the rapid development of advanced nanotechnologies to effectively harness solar power. The construction of photosynthetic biohybrid systems (PBSs) aims to link preassembled biosynthetic pathways with inorganic light absorbers. This strategy inherits both the high light-harvesting efficiency of solid-state semiconductors and the superior catalytic performance of whole-cell microorganisms.

Physical Biology of the Materials-Microorganism Interface.

Future solar-to-chemical production will rely upon a deep understanding of the material-microorganism interface. Hybrid technologies, which combine inorganic semiconductor light harvesters with biological catalysis to transform light, air, and water into chemicals, already demonstrate a wide product scope and energy efficiencies surpassing that of natural photosynthesis. But optimization to economic competitiveness and fundamental curiosity beg for answers to two basic questions: (1) how do materials transfer energy and charge to microorganisms, and (2) how do we design for bio- and chemocompatibility between these seemingly unnatural partners? This Perspective highlights the state-of-the-art and outlines future research paths to inform the cadre of spectroscopists, electrochemists, bioinorganic chemists, material scientists, and biologists who will ultimately solve these mysteries.

Biological-inorganic hybrid systems as a generalized platform for chemical production.

An expanding renewable energy market to supplant petrochemicals has motivated synthesis technologies that use renewable feedstocks, such as CO. Hybrid biological-inorganic systems provide a sustainable, efficient, versatile, and inexpensive chemical synthesis platform. These systems comprise biocompatible electrodes that transduce electrical energy either directly or indirectly into bioavailable energy, such as H and NAD(P)H.

Cyborgian Material Design for Solar Fuel Production: The Emerging Photosynthetic Biohybrid Systems.

Photosynthetic biohybrid systems (PBSs) combine the strengths of inorganic materials and biological catalysts by exploiting semiconductor broadband light absorption to capture solar energy and subsequently transform it into valuable CO-derived chemicals by taking advantage of the metabolic pathways in living organisms. In this work, we first traverse through a brief history of recent PBSs, demonstrating the modularity and diversity of possible architectures to rival and, in many cases, surpass the performance of chemistry or biology alone before envisioning the future of these hybrid systems, opportunities for improvement, and its role in sustainable living here on earth and beyond.

Ambient nitrogen reduction cycle using a hybrid inorganic-biological system.

We demonstrate the synthesis of NH from N and HO at ambient conditions in a single reactor by coupling hydrogen generation from catalytic water splitting to a H-oxidizing bacterium , which performs N and CO reduction to solid biomass. Living cells of may be directly applied as a biofertilizer to improve growth of radishes, a model crop plant, by up to ∼1,440% in terms of storage root mass. The NH generated from nitrogenase (Nase) in can be diverted from biomass formation to an extracellular ammonia production with the addition of a glutamate synthetase inhibitor.

Spectroscopic elucidation of energy transfer in hybrid inorganic-biological organisms for solar-to-chemical production.

The rise of inorganic-biological hybrid organisms for solar-to-chemical production has spurred mechanistic investigations into the dynamics of the biotic-abiotic interface to drive the development of next-generation systems. The model system, Moorella thermoacetica-cadmium sulfide (CdS), combines an inorganic semiconductor nanoparticle light harvester with an acetogenic bacterium to drive the photosynthetic reduction of CO to acetic acid with high efficiency. In this work, we report insights into this unique electrotrophic behavior and propose a charge-transfer mechanism from CdS to M.

Cysteine-Cystine Photoregeneration for Oxygenic Photosynthesis of Acetic Acid from CO2 by a Tandem Inorganic-Biological Hybrid System.

Tandem "Z-scheme" approaches to solar-to-chemical production afford the ability to independently develop and optimize reductive photocatalysts for CO2 reduction to multicarbon compounds and oxidative photocatalysts for O2 evolution. To connect the two redox processes, molecular redox shuttles, reminiscent of biological electron transfer, offer an additional level of facile chemical tunability that eliminates the need for solid-state semiconductor junction engineering. In this work, we report a tandem inorganic-biological hybrid system capable of oxygenic photosynthesis of acetic acid from CO2.

Self-photosensitization of nonphotosynthetic bacteria for solar-to-chemical production.

Improving natural photosynthesis can enable the sustainable production of chemicals. However, neither purely artificial nor purely biological approaches seem poised to realize the potential of solar-to-chemical synthesis. We developed a hybrid approach, whereby we combined the highly efficient light harvesting of inorganic semiconductors with the high specificity, low cost, and self-replication and -repair of biocatalysts.

Nanowire-bacteria hybrids for unassisted solar carbon dioxide fixation to value-added chemicals.

Direct solar-powered production of value-added chemicals from CO2 and H2O, a process that mimics natural photosynthesis, is of fundamental and practical interest. In natural photosynthesis, CO2 is first reduced to common biochemical building blocks using solar energy, which are subsequently used for the synthesis of the complex mixture of molecular products that form biomass. Here we report an artificial photosynthetic scheme that functions via a similar two-step process by developing a biocompatible light-capturing nanowire array that enables a direct interface with microbial systems.

Artificial photosynthesis for sustainable fuel and chemical production.

The apparent incongruity between the increasing consumption of fuels and chemicals and the finite amount of resources has led us to seek means to maintain the sustainability of our society. Artificial photosynthesis, which utilizes sunlight to create high-value chemicals from abundant resources, is considered as the most promising and viable method. This Minireview describes the progress and challenges in the field of artificial photosynthesis in terms of its key components: developments in photoelectrochemical water splitting and recent progress in electrochemical CO2 reduction.

Salt-induced self-assembly of bacteria on nanowire arrays.

Studying bacteria-nanostructure interactions is crucial to gaining controllable interfacing of biotic and abiotic components in advanced biotechnologies. For bioelectrochemical systems, tunable cell-electrode architectures offer a path toward improving performance and discovering emergent properties. As such, Sporomusa ovata cells cultured on vertical silicon nanowire arrays formed filamentous cells and aligned parallel to the nanowires when grown in increasing ionic concentrations.

Controlled doping of carbon nanotubes with metallocenes for application in hybrid carbon nanotube/Si solar cells.

There is considerable interest in the controlled p-type and n-type doping of carbon nanotubes (CNT) for use in a range of important electronics applications, including the development of hybrid CNT/silicon (Si) photovoltaic devices. Here, we demonstrate that easy to handle metallocenes and related complexes can be used to both p-type and n-type dope single-walled carbon nanotube (SWNT) thin films, using a simple spin coating process. We report n-SWNT/p-Si photovoltaic devices that are >450 times more efficient than the best solar cells of this type currently reported and show that the performance of both our n-SWNT/p-Si and p-SWNT/n-Si devices is related to the doping level of the SWNT.