Femtosecond Photodynamics
of the Red/Green Cyanobacteriochrome NpR6012g4 from <i>Nostoc
punctiforme</i>. 1. Forward Dynamics
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Abstract
Phytochromes are well-known red/far-red photosensory
proteins that utilize the photoisomerization of a linear tetrapyrrole
(bilin) chromophore to detect the ratio of red to far-red light. Cyanobacteriochromes
(CBCRs) are related photosensory proteins with a bilin-binding GAF
domain, but much more diverse spectral sensitivity, with five recognized
subfamilies of CBCRs described to date. The mechanisms that underlie
this spectral diversity have not yet been fully elucidated. One of
the main CBCR subfamilies photoconverts between a red-absorbing ground
state, like the familiar P<sub>r</sub> state of phytochromes, and
a green-absorbing photoproduct (P<sub>g</sub>). Here, we examine the
ultrafast forward photodynamics of the red/green CBCR NpR6012g4 from
the <i>NpR6012</i> locus of the nitrogen-fixing cyanobacterium <i>Nostoc punctiforme</i>. Using transient absorption spectroscopy
with broadband detection and multicomponent global analysis, we observed
multiphasic
excited-state dynamics that induces the forward reaction (red-absorbing
to green-absorbing), which we interpret as arising from ground-state
heterogeneity. Excited-state decays with lifetimes of 55 and 345 ps
generate the primary photoproduct (Lumi-R), and the fastest decay
(5 ps) did not produce Lumi-R. Although the photoinduced kinetics
of Npr6012g4 is comparable with that of the Cph1 phytochrome isolated
from <i>Synechocystis</i> cyanobacteria, NpR6012g4 exhibits
a ≥2–3-fold higher photochemical quantum yield. Understanding
the structural basis of this enhanced quantum yield may prove to be
useful in increasing the photochemical efficiency of other bilin-based
photosensors