4.6 Article

The impact of chromophore choice on the assembly kinetics and primary photochemistry of a red/green cyanobacteriochrome

Journal

PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 23, Issue 37, Pages 20867-20874

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/d1cp02696h

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Funding

  1. Swiss National Science Foundation (SNF) [200020B 188694/1]

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Cyanobacteriochromes (CBCRs) are photoreceptor proteins with potential for biotechnological applications, some of which can bind both phycocyanobilin (PCB) and biliverdin (BV). The assembly kinetics of CBCR AmI-g2 with both chromophores were studied, revealing that the assembly reaction with PCB is faster than with BV, where the formation of a non-covalent intermediate is the rate-limiting step. Photochemical quantum yields of forward and backward reactions of AmI-g2 were estimated and discussed in comparison with homologous CBCRs.
Cyanobacteriochromes (CBCRs) are bi-stable photoreceptor proteins with high potential for biotechnological applications. Most of these proteins utilize phycocyanobilin (PCB) as a light-sensing co-factor, which is unique to cyanobacteria, but some variants also incorporate biliverdin (BV). The latter are of particular interest for biotechnology due to the natural abundance and red-shifted absorption of BV. Here, AmI-g2 was investigated, a CBCR capable of binding both PCB and BV. The assembly kinetics and primary photochemistry of AmI-g2 with both chromophores were studied in vitro. The assembly reaction with PCB is roughly 10x faster than BV, and the formation of a non-covalent intermediate was identified as the rate-limiting step in the case of BV. This step is fast for PCB, where the formation of the covalent thioether bond between AmI-g2 and PCB becomes rate-limiting. The photochemical quantum yields of the forward and backward reactions of AmI-g2 were estimated and discussed in the context of homologous CBCRs.

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