Shunts,
alternative
pathways
in
chemical
reaction
networks,
are
ubiquitous
Nature,
enabling
adaptability
to
external
and
internal
stimuli.
We
introduce
a
network
(CRN)
which
the
recovery
of
Michael-accepting
species
is
driven
by
oxidation
chemistry.
Using
weak
oxidants
can
enable
access
two
shunts
within
this
CRN
with
different
kinetics
reduced
number
side
reactions
compared
main
cycle
that
strong
oxidants.
Further,
we
strategy
recycle
one
products
under
flow
conditions
partially
reverse
control
product
speciation
throughout
time.
These
findings
new
levels
over
artificial
CRNs,
redox
chemistry,
narrowing
gap
between
synthetic
natural
systems.
ChemCatChem,
Journal Year:
2022,
Volume and Issue:
15(4)
Published: Dec. 31, 2022
Abstract
H
2
‐producing,
submarine
hydrothermal
vents
present
a
plausible
environment
for
the
prebiotic
synthesis
of
first
organic
compounds
at
emergence
life.
Geochemical
CO
reduction
these
vent
systems
harbors
similarity
to
ancient,
biochemical
acetyl‐CoA
pathway
fixation
in
modern
autotrophs.
Both
pathways
involve
catalytic
transformations
with
transition
metals
as
active
centers.
This
concept
article
provides
some
insight
about
origins
life,
mineral‐catalyzed
reduction,
and
its
correlation
enzymatic
by
focusing
on
key
studies.
Chemical Science,
Journal Year:
2023,
Volume and Issue:
14(48), P. 14100 - 14108
Published: Jan. 1, 2023
A
nonenzymatic
reaction
converting
pyruvate
to
phosphoenolpyruvate
(PEP)
is
shown
proceed
through
carboxylate
phosphorylation,
suggesting
that
only
a
single
phosphorylation
mechanism
was
needed
initiate
metabolic
networks.
The
relationship
between
genetic
molecules
and
metabolism
is
one
of
the
longest
standing
problems
for
origin
life.
A
central
molecule
within
early
coenzyme
nicotinamide
adenine
dinucleotide
(NAD(H)),
a
modified
ribonucleotide
reducing
agent.
Yet,
without
enzymes,
NADH
does
not
reduce
carbonyl
compounds,
its
primary
metabolic
substrates,
leading
to
an
apparent
paradox
regarding
role
in
evolution
metabolism.
We
now
report
that
abundant
metal
ions
turn
on
nonenzymatic,
stereoselective,
potentially
primordial
reduction
reaction
keto
acids
by
NADH.
Kinetic,
mechanistic,
computational
studies
elucidate
mechanism
way
stereochemistry
transferred.
Complexes
metals
with
RNA-derived
coenzymes
could
have
mediated
transition
from
inorganic
organic
agents
propagation
chirality
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
64(2)
Published: Nov. 19, 2024
Abstract
Numerous
reactions
within
metabolic
pathways
have
been
reported
to
occur
nonenzymatically,
supporting
the
hypothesis
that
life
arose
upon
a
primitive
nonenzymatic
precursor
metabolism.
However,
most
of
those
studies
reproduce
individual
transformations
or
segments
without
providing
common
set
conditions
for
classes
span
multiple
pathways.
In
this
study,
we
search
across
recurring
chemical
transformation
in
metabolism:
alkene
hydration.
The
mild
identify
(Fe
oxides
such
as
green
rust)
apply
all
hydration
rTCA
cycle
and
gluconeogenesis,
including
phosphoenolpyruvate
(PEP)
2‐phosphoglycerate
(2PGA),
which
had
not
previously
under
conditions.
Mechanistic
insights
were
obtained
by
studying
analogous
substrates
through
anoxic
radical
trapping
experiments.
Searching
provides
complementary
strategy
triangulate
conducive
emergence
protometabolism.
Shunts,
alternative
pathways
in
chemical
reaction
networks,
are
ubiquitous
Nature,
enabling
adaptability
to
external
and
internal
stimuli.
We
introduce
a
network
(CRN)
which
the
recovery
of
Michael-accepting
species
is
driven
by
oxidation
chemistry.
Using
weak
oxidants
can
enable
access
two
shunts
within
this
CRN
with
different
kinetics
reduced
number
side
reactions
compared
main
cycle
that
strong
oxidants.
Further,
we
strategy
recycle
one
products
under
flow
conditions
partially
reverse
control
product
speciation
throughout
time.
These
findings
new
levels
over
artificial
CRNs,
redox
chemistry,
narrowing
gap
between
synthetic
natural
systems.
