Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(31), С. 17164 - 17175
Опубликована: Июль 13, 2023
One
of
the
hallmarks
multicomponent
metal-organic
frameworks
(MOFs)
is
to
finely
tune
their
active
centers
achieve
product
selectivity.
In
particular,
obtaining
bimetallic
MOF
hollow
structures
with
precisely
tailored
redox
under
same
topology
still
challenging
despite
a
recent
surge
such
efforts.
Herein,
we
present
an
engineering
strategy
named
"cluster
labilization"
generate
hierarchically
porous
composites
and
tunable
centers.
By
partially
replacing
zirconium
cerium
in
hexanuclear
clusters
UiO-66,
unevenly
distributed
yolk-shell
(YSS)
were
formed.
Through
acid
treatment
or
annealing
YSS
precursor,
single-shell
(SSHS)
double-shell
(DSHS)
can
be
obtained,
respectively.
The
SSHS
DSHS
differ
species,
valence,
spatial
locations.
More
importantly,
YSS,
SSHS,
distinct
microenvironments
exhibit
catalytic
activity,
reversed
selectivity,
high
stability
tandem
reaction
photoreaction.
Chemical Reviews,
Год журнала:
2023,
Номер
123(9), С. 5347 - 5420
Опубликована: Апрель 12, 2023
Enzymatic
catalysis
has
fueled
considerable
interest
from
chemists
due
to
its
high
efficiency
and
selectivity.
However,
the
structural
complexity
vulnerability
hamper
application
potentials
of
enzymes.
Driven
by
practical
demand
for
chemical
conversion,
there
is
a
long-sought
quest
bioinspired
catalysts
reproducing
even
surpassing
functions
natural
As
nanoporous
materials
with
surface
areas
crystallinity,
metal-organic
frameworks
(MOFs)
represent
an
exquisite
case
how
enzymes
their
active
sites
are
integrated
into
porous
solids,
affording
heterogeneous
superior
stability
customizable
structures.
In
this
review,
we
comprehensively
summarize
advances
MOFs
catalysis,
discuss
design
principle
various
MOF-based
catalysts,
such
as
MOF-enzyme
composites
embedded
sites,
explore
utility
these
in
different
reactions.
The
advantages
enzyme
mimetics
also
highlighted,
including
confinement,
templating
effects,
functionality,
comparison
homogeneous
supramolecular
catalysts.
A
perspective
provided
potential
solutions
addressing
current
challenges
MOF
catalysis.
Chemical Society Reviews,
Год журнала:
2022,
Номер
51(18), С. 7810 - 7882
Опубликована: Янв. 1, 2022
Although
C–H
functionalization
is
one
of
the
simplest
reactions,
it
requires
use
highly
active
and
selective
catalysts.
Recently,
C–H-active
transformations
using
porous
materials
such
as
crystalline
metal-organic
frameworks
(MOFs)
covalent-organic
(COFs)
well
amorphous
porous-organic
polymers
(POPs)
new
emerging
heterogeneous
catalysts
have
attracted
significant
attention
due
to
their
promising
activity
potential
material
tunability.
These
solids
offer
exceptional
structural
uniformity,
facile
tunability
permanent
porosity.
In
addition,
tuning
catalytic
selectivity
these
can
be
achieved
through
engineering
site
microenvironments,
metal
node
substitution,
linker
changes,
node/linker
functionalization,
pore
modification.
The
present
review
provides
an
overview
current
state
art
on
MOFs,
COFs
POPs
advanced
for
various
bond
activation
providing
details
about
chemo-,
regio-,
stereo-selectivity
control,
comparing
performance
with
that
other
catalysts,
triggering
additional
research
by
showing
limitations
challenges
in
this
area,
a
perspective
future
developments.
Analytical Chemistry,
Год журнала:
2022,
Номер
94(11), С. 4821 - 4830
Опубликована: Март 9, 2022
Biomimic
nanozymes
coassembled
by
peptides
or
proteins
and
small
active
molecules
provide
an
effective
strategy
to
design
attractive
nanozymes.
Although
some
promising
have
been
reported,
rational
regulation
for
higher
catalytic
activity
of
biomimic
remains
challenging.
Hence,
we
proposed
a
novel
nanozyme
encapsulating
the
coassembly
hemin/bovine
serum
albumin
(BSA)
in
zeolite
imidazolate
frameworks
(ZIF-8)
achieve
controllable
tailoring
peroxidase-like
via
confinement
effect.
The
assembly
Hemin@BSA
was
inspired
structure
horseradish
peroxidase
(HRP),
which
hemin
served
as
cofactor
surrounded
BSA
blocking
pocket
construct
favorable
hydrophobic
space
substrate
enrichment.
Benefiting
from
effect,
ZIF-8
with
porous
intracavity
identified
ideal
outer
layer
accelerate
transport
internal
circulation
catalysis,
significantly
enhancing
its
activity.
Especially,
precise
encapsulation
could
also
prevent
it
decomposition
harsh
environments
rapid
crystallization
around
form
protective
shell.
Based
on
improved
Hemin@BSA@ZIF-8,
several
applications
were
successfully
performed
sensitive
detection
including
H2O2,
glucose,
bisphenol
A
(BPA).
Satisfactory
results
highlight
that
using
encapsulate
offers
very
successful
improve
stability
nanozymes,
broadening
potential
application
biocatalytic
metal-organic
(MOFs).
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(39)
Опубликована: Авг. 2, 2022
Abstract
Enzyme
immobilization
is
essential
to
the
commercial
viability
of
various
critical
large‐scale
biocatalytic
processes.
However,
challenges
remain
for
systems,
such
as
difficulties
in
loading
large
enzymes,
enzyme
leaching,
and
limitations
fabrication.
Herein,
we
describe
a
green
scalable
strategy
prepare
high‐performance
biocatalysts
through
situ
assembly
enzymes
with
covalent
organic
frameworks
(COFs)
under
ambient
conditions
(aqueous
solution
room
temperature).
The
obtained
have
exceptional
reusability
stability
serve
efficient
important
industrial
reactions
that
cannot
be
efficiently
catalyzed
by
free
or
traditional
systems.
Notably,
this
versatile
platform
applicable
COFs
enzymes.
an
aqueous
occurred
within
short
timeframe
(ca.
10–30
min)
could
scaled
up
readily
2.3
g
per
reaction).
Processes,
Год журнала:
2022,
Номер
10(3), С. 494 - 494
Опубликована: Март 1, 2022
Enzymes
are
outstanding
(bio)catalysts,
not
solely
on
account
of
their
ability
to
increase
reaction
rates
by
up
several
orders
magnitude
but
also
for
the
high
degree
substrate
specificity,
regiospecificity
and
stereospecificity.
The
use
development
enzymes
as
robust
biocatalysts
is
one
main
challenges
in
biotechnology.
However,
despite
specificities
turnover
enzymes,
there
drawbacks.
At
industrial
level,
these
drawbacks
typically
overcome
resorting
immobilized
enhance
stability.
Immobilization
allows
reuse,
increases
stability,
facilitates
process
control,
eases
product
recovery,
enhances
yield
quality.
This
especially
important
expensive
those
obtained
low
fermentation
with
relatively
activity.
review
provides
an
integrated
perspective
(multi)enzyme
immobilization
that
abridges
a
critical
evaluation
methods
carriers,
biocatalyst
metrics,
impact
key
carrier
features
performance,
trends
towards
miniaturization
detailed
illustrative
examples
representative
biocatalytic
applications
promoting
sustainability.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(21)
Опубликована: Март 10, 2022
Controllable
regulations
on
the
enzyme
conformation
to
optimize
catalytic
performance
are
highly
desired
for
immobilized
biocatalysts
yet
remain
challenging.
Covalent
organic
frameworks
(COFs)
possess
confined
channels
with
finely
tunable
pore
environment,
offering
a
promising
platform
encapsulation.
Herein,
we
covalently
cytochrome
c
(Cyt
c)
in
size-matched
of
COFs
different
contents
anchoring
site,
and
significant
enhancement
stability
activity
(≈600
%
relative
compared
free
enzyme)
can
be
realized
by
optimizing
covalent
interactions.
Structural
analyses
Cyt
suggest
that
bonding
could
induce
conformational
perturbation
resulting
more
accessible
active
sites.
The
effectiveness
interaction
modulation
together
tailorable
offers
promise
develop
high-performance
biocatalysts.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(24), С. 13469 - 13475
Опубликована: Июнь 7, 2023
Immobilization
of
fragile
enzymes
in
crystalline
porous
materials
offers
new
opportunities
to
expand
the
applications
biocatalysts.
However,
limited
by
pore
size
and/or
harsh
synthesis
conditions
hosts,
often
suffer
from
dimension
limitation
or
denaturation
during
immobilization
process.
Taking
advantage
dynamic
covalent
chemistry
feature
organic
frameworks
(COFs),
herein,
we
report
a
preprotection
strategy
encapsulate
COFs
self-repairing
and
crystallization
Enzymes
were
first
loaded
low-crystalline
polymer
networks
with
mesopores
formed
at
initial
growth
stage,
which
could
offer
effective
protection
for
reaction
conditions,
subsequently
encapsulation
proceeded
disordered
into
framework.
Impressively,
biological
activity
can
be
well-maintained
after
encapsulation,
obtained
enzyme@COFs
also
show
superior
stability.
Furthermore,
circumvents
enzymes,
its
versatility
was
verified
different
sizes
surface
charges,
as
well
two-enzyme
cascade
system.
This
study
universal
design
idea
robust
supports
holds
promise
developing
high-performance
immobilized
