The
fabrication
of
self-driven
systems
with
flexibility
and
tunable
output
for
organic
photoinduction
is
highly
desirable
but
challenging.
In
this
study,
a
3D
cadmium
metal-organic
framework
(Cd-MOF)
synthesized
used
as
filler
ethyl
cellulose
(EC)
to
create
mechanically
durable
flexible
Cd-MOF@EC
composite
films.
Due
its
well-established
platform
periodically
precise
structure
nature,
the
outputs
Cd-MOF-based
TENG
are
much
higher
than
those
ligand-based
TENGs.
Furthermore,
films
different
doping
ratios
Cd-MOF
employed
assemble
Cd-MOF@EC-based
triboelectric
nanogenerators
(TENGs).
results
reveal
that
ratio
10
wt.%
in
provides
highest
output.
Subsequently,
(FCEC-TENG),
working
contact-separation
model,
constructed
harvest
mechanical
energy
from
human
body,
demonstrating
excellent
performance
stability.
harvested
FCEC-TENG
can
directly
illuminate
14
commercial
white
light-emitting
diodes
(LEDs),
providing
visible
light
bromination
reaction,
generating
bromide
good
yield
tolerance.
This
study
presents
an
effective
method
constructing
MOF-based
self-powered
photoinduced
transformation
systems.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(41), С. 19097 - 19105
Опубликована: Окт. 4, 2022
Selective
functionalization
of
aliphatic
C–H
bonds,
ubiquitous
in
molecular
structures,
could
allow
ready
access
to
diverse
chemical
products.
While
enzymatic
oxygenation
bonds
is
well
established,
the
analogous
nitrogen
still
unknown;
nature
reliant
on
preoxidized
compounds
for
incorporation.
Likewise,
synthetic
methods
selective
derivatization
unbiased
remain
elusive.
In
this
work,
new-to-nature
heme-containing
nitrene
transferases
were
used
as
starting
points
directed
evolution
enzymes
selectively
aminate
and
amidate
unactivated
C(sp3)–H
sites.
The
desymmetrization
methyl-
ethylcyclohexane
with
divergent
site
selectivity
offered
demonstration.
evolved
these
lineages
are
highly
promiscuous
show
activity
toward
a
wide
array
substrates,
providing
foundation
further
transferase
function.
Computational
studies
kinetic
isotope
effects
(KIEs)
consistent
stepwise
radical
pathway
involving
an
irreversible,
enantiodetermining
hydrogen
atom
transfer
(HAT),
followed
by
lower-barrier
diastereoselectivity-determining
rebound
step.
In-enzyme
dynamics
(MD)
simulations
reveal
predominantly
hydrophobic
pocket
favorable
dispersion
interactions
substrate.
By
offering
direct
path
from
saturated
precursors,
present
new
biochemical
logic
accessing
nitrogen-containing
compounds.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(13)
Опубликована: Янв. 27, 2024
Biocatalytic
oxidations
are
an
emerging
technology
for
selective
C-H
bond
activation.
While
promising
a
range
of
oxidations,
practical
use
enzymes
catalyzing
aerobic
hydroxylation
is
presently
limited
by
their
substrate
scope
and
stability
under
industrially
relevant
conditions.
Here,
we
report
the
engineering
application
non-heme
iron
α-ketoglutarate-dependent
dioxygenase
direct
stereo-
regio-selective
non-native
fluoroindanone
en
route
to
oncology
treatment
belzutifan,
replacing
five-step
chemical
synthesis
with
enantioselective
hydroxylation.
Mechanistic
studies
indicated
that
formation
desired
product
was
enzyme
overoxidation,
these
properties
subsequently
improved
directed
evolution,
yielding
biocatalyst
capable
>15,000
total
turnovers.
Highlighting
industrial
utility
this
biocatalyst,
high-yielding,
green,
efficient
oxidation
demonstrated
at
kilogram
scale
belzutifan.
ACS Catalysis,
Год журнала:
2023,
Номер
13(7), С. 4853 - 4865
Опубликована: Март 27, 2023
Modified
amino
acids
are
important
building
blocks
in
both
natural
biomolecules
and
synthetic
small-molecule
drugs.
Here,
we
review
the
roles
of
iron-
α-ketoglutarate-dependent
dioxygenases
oxidative
modification
acids,
focusing
on
C–H
hydroxylation
halogenation.
Recent
engineering
approaches
to
alter
substrate
specificity,
improve
catalytic
efficiency,
install
non-native
activities
also
discussed,
along
with
several
applications
complex
molecule
synthesis.
We
conclude
a
brief
discussion
recent
discoveries
unique
cyclization
by
family
members
contemporary
challenges
expanding
biocatalytic
utility
reaction
scope
enzyme
family.
Chemical Reviews,
Год журнала:
2023,
Номер
123(16), С. 10381 - 10431
Опубликована: Июль 31, 2023
The
ability
to
site-selectively
modify
equivalent
functional
groups
in
a
molecule
has
the
potential
streamline
syntheses
and
increase
product
yields
by
lowering
step
counts.
Enzymes
catalyze
site-selective
transformations
throughout
primary
secondary
metabolism,
but
leveraging
this
capability
for
non-native
substrates
reactions
requires
detailed
understanding
of
limitations
enzyme
catalysis
how
these
bounds
can
be
extended
protein
engineering.
In
review,
we
discuss
representative
examples
involving
group
manipulation
C-H
bond
functionalization.
We
include
illustrative
native
catalysis,
our
focus
is
on
cases
often
using
engineered
enzymes.
then
use
enzymes
chemoenzymatic
target-oriented
synthesis
conclude
with
survey
tools
techniques
that
could
expand
scope
catalysis.
JACS Au,
Год журнала:
2024,
Номер
4(6), С. 2068 - 2080
Опубликована: Май 31, 2024
Biocatalysis
is
currently
undergoing
a
profound
transformation.
The
field
moves
from
relying
on
nature's
chemical
logic
to
discipline
that
exploits
generic
activation
modes,
allowing
for
novel
biocatalytic
reactions
and,
in
many
instances,
entirely
new
chemistry.
Generic
modes
enable
wide
range
of
reaction
types
and
played
pivotal
role
advancing
the
fields
organo-
photocatalysis.
This
perspective
aims
summarize
principal
harnessed
enzymes
develop
biocatalysts.
Although
extensively
researched
past,
highlighted
when
applied
within
enzyme
active
sites,
facilitate
transformations
have
largely
eluded
efficient
selective
catalysis.
advance
attributed
multiple
tunable
interactions
substrate
binding
pocket
precisely
control
competing
pathways
transition
states.
We
will
highlight
cases
synthetic
methodologies
achieved
by
engineered
provide
insights
into
potential
future
developments
this
rapidly
evolving
field.
