Angewandte Chemie,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 10, 2025
Abstract
Lactiplantibacillus
plantarum
is
known
to
utilize
exogenous
small
molecule
quinone
mediators
perform
extracellular
electron
transfer
(EET),
allowing
it
produce
a
detectable
current
in
bioelectrochemical
system
(BES).
Utilization
of
by
L.
requires
type‐II
NADH
dehydrogenase
(Ndh2);
however,
structural
variations
the
core
1,4‐naphthoquinone
EET
have
shown
yield
significantly
different
outputs.
Herein,
we
assembled
library
40
quinone‐based
probe
important
physicochemical
properties
and
biochemical
interactions
responsible
for
Ndh2‐dependent
.
The
was
designed
with
inspiration
from
naturally
occurring
metabolites,
assembly
focused
on
modifications
that
diversified
polarity,
reduction
potential,
predicted
free
energy
binding
Ndh2
(ΔG
comp
),
as
these
are
hypothesized
drive
activity.
In
general,
activity
an
iron(III)
nanoparticle
assay
correlates
mediator's
polarity
ΔG
Five
were
analyzed
BESs
,
each
generated
over
background
signal.
Importantly,
amine‐containing
mediator
yielded
incredibly
stable
output
course
experiment
(up
5
days).
These
findings
improve
our
understanding
structure‐activity
relationships
quinone‐mediated
provide
bioelectronic
sensing
applications.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Dec. 21, 2023
Abstract
Microelectronic
devices
can
directly
communicate
with
biology,
as
electronic
information
be
transmitted
via
redox
reactions
within
biological
systems.
By
engineering
biology’s
native
networks,
we
enable
interrogation
and
control
of
systems
at
several
hierarchical
levels:
proteins,
cells,
cell
consortia.
First,
electro-biofabrication
facilitates
on-device
component
assembly.
Then,
electrode-actuated
data
transmission
redox-linked
synthetic
biology
allows
programming
enzyme
activity
closed-loop
electrogenetic
cellular
function.
Specifically,
horseradish
peroxidase
is
assembled
onto
interdigitated
electrodes
where
electrode-generated
hydrogen
peroxide
controls
its
activity.
E.
coli
’s
stress
response
regulon,
oxyRS
,
rewired
to
algorithm-based
feedback
gene
expression,
including
an
eCRISPR
module
that
switches
cell-cell
quorum
sensing
communication
from
one
autoinducer
another—creating
electronically
controlled
‘bilingual’
cell.
these
disparate
redox-guided
are
wirelessly
connected,
enabling
real-time
user-based
control.
We
suggest
methodologies
will
help
us
better
understand
develop
sophisticated
for
biology.
Angewandte Chemie International Edition,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 10, 2025
Lactiplantibacillus
plantarum
is
known
to
utilize
exogenous
small
molecule
quinone
mediators
perform
extracellular
electron
transfer
(EET),
allowing
it
produce
a
detectable
current
in
bioelectrochemical
system
(BES).
Utilization
of
by
L.
requires
type-II
NADH
dehydrogenase
(Ndh2);
however,
structural
variations
the
core
1,4-naphthoquinone
EET
have
shown
yield
significantly
different
outputs.
Herein,
we
assembled
library
40
quinone-based
probe
important
physicochemical
properties
and
biochemical
interactions
responsible
for
Ndh2-dependent
plantarum.
The
was
designed
with
inspiration
from
naturally
occurring
metabolites,
assembly
focused
on
modifications
that
diversified
polarity,
reduction
potential,
predicted
free
energy
binding
Ndh2
(ΔGcomp),
as
these
are
hypothesized
drive
activity.
In
general,
activity
an
iron(III)
nanoparticle
assay
correlates
mediator's
polarity
ΔGcomp.
Five
were
analyzed
BESs
plantarum,
each
generated
over
background
signal.
Importantly,
amine-containing
mediator
yielded
incredibly
stable
output
course
experiment
(up
5
days).
These
findings
improve
our
understanding
structure-activity
relationships
quinone-mediated
provide
bioelectronic
sensing
applications.
Frontiers in Chemistry,
Journal Year:
2025,
Volume and Issue:
13
Published: March 12, 2025
Mineral-respiring
microorganisms
from
hydrothermal
vents
to
terrestrial
soils
express
filaments
that
electrically
connect
intracellular
respiration
extracellular
geochemistry.
Filaments
dubbed
“cytochrome
nanowires”
(CNs)
have
been
resolved
by
CryoEM,
but
whether
they
are
the
two-decades-long
sought-after
physiological
“nanowires”
remains
unproven.
To
assess
their
functional
competence,
we
analyzed
biological
redox
conduction
in
all
CNs
computing
driving
forces
presence
of
anti-cooperativities,
reorganization
energies
with
electronic
polarizability,
and
Marcus
rates
for
diffusive
protein-limited
flux
models.
The
chain
heme
cofactors
any
CN
must
be
densely
packed
realize
weak
(≤0.01
eV)
coupling
electron
transfer,
as
evidenced
a
single
Soret
band
produced
coincidental
absorptions
on
multiple
hemes.
Dense
packing,
turn,
has
three
consequences:
(1)
limited
(≤|0.3|
due
shared
electrostatic
microenvironments,
(2)
strong
(≤0.12
anti-cooperativities
would
accentuate
free
energy
landscape
if
linear
arrangement
did
not
dictate
contra-thermodynamic
oxidation
order,
(3)
an
entropic
penalty
is
offset
thioether
‘tethers’
hemes
protein
backbone.
These
linkages
physically
necessitate
rate-throttling
T-stacked
motif
(10-fold
slower
than
other
highly
conserved
slip-stacked
motif).
If
sequence
slip-
had
fastest
known
nanosecond
at
every
step,
micron-long
filament
carry
0.02
pA
current
0.1
V,
or
0.2
pA.
Actual
sub-optimal
(≤10
2
-fold
lower),
sufficient
conductivities
cellular
respiration,
most
thousands
needed
total
metabolic
flux.
Reported
once
used
argue
metallic-like
pili
against
cytochrome
hypothesis
now
attributed
remain
inconsistent
10
–10
5
physical
constraints
through
multiheme
architectures.
Angewandte Chemie,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 10, 2025
Abstract
Lactiplantibacillus
plantarum
is
known
to
utilize
exogenous
small
molecule
quinone
mediators
perform
extracellular
electron
transfer
(EET),
allowing
it
produce
a
detectable
current
in
bioelectrochemical
system
(BES).
Utilization
of
by
L.
requires
type‐II
NADH
dehydrogenase
(Ndh2);
however,
structural
variations
the
core
1,4‐naphthoquinone
EET
have
shown
yield
significantly
different
outputs.
Herein,
we
assembled
library
40
quinone‐based
probe
important
physicochemical
properties
and
biochemical
interactions
responsible
for
Ndh2‐dependent
.
The
was
designed
with
inspiration
from
naturally
occurring
metabolites,
assembly
focused
on
modifications
that
diversified
polarity,
reduction
potential,
predicted
free
energy
binding
Ndh2
(ΔG
comp
),
as
these
are
hypothesized
drive
activity.
In
general,
activity
an
iron(III)
nanoparticle
assay
correlates
mediator's
polarity
ΔG
Five
were
analyzed
BESs
,
each
generated
over
background
signal.
Importantly,
amine‐containing
mediator
yielded
incredibly
stable
output
course
experiment
(up
5
days).
These
findings
improve
our
understanding
structure‐activity
relationships
quinone‐mediated
provide
bioelectronic
sensing
applications.
