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

Abstract:

: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 CO2 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. thermoacetica Transient absorption (TA) spectroscopy revealed that photoexcited electron transfer rates increase with increasing hydrogenase (H2ase) enzyme activity. On the same time scale as the TA spectroscopy, time-resolved infrared (TRIR) spectroscopy showed spectral changes in the 1,700-1,900-cm-1 spectral region. The quantum efficiency of this system for photosynthetic acetic acid generation also increased with increasing H2ase activity and shorter carrier lifetimes when averaged over the first 24 h of photosynthesis. However, within the initial 3 h of photosynthesis, the rate followed an opposite trend: The bacteria with the lowest H2ase activity photosynthesized acetic acid the fastest. These results suggest a two-pathway mechanism: a high quantum efficiency charge-transfer pathway to H2ase generating H2 as a molecular intermediate that dominates at long time scales (24 h), and a direct energy-transducing enzymatic pathway responsible for acetic acid production at short time scales (3 h). This work represents a promising platform to utilize conventional spectroscopic methodology to extract insights from more complex biotic-abiotic hybrid systems.

authors

Kornienko N,Sakimoto KK,Herlihy DM,Nguyen SC,Alivisatos AP,Harris CB,Schwartzberg A,Yang P

doi

10.1073/pnas.1610554113

subject

Has Abstract

pub_date

2016-10-18 00:00:00

pages

11750-11755

issue

42

eissn

0027-8424

issn

1091-6490

pii

1610554113

journal_volume

113

pub_type

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