Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(22)
Published: April 1, 2024
Abstract
The
design
and
orderly
layered
co‐immobilization
of
multiple
enzymes
on
resin
particles
remain
challenging.
In
this
study,
the
SpyTag/SpyCatcher
binding
pair
was
fused
to
N‐terminus
an
alcohol
dehydrogenase
(ADH)
aldo‐keto
reductase
(AKR),
respectively.
A
non‐canonical
amino
acid
(ncAA),
p
‐azido‐L‐phenylalanine
(p‐AzF),
as
anchor
for
covalent
bonding
enzymes,
genetically
inserted
into
preselected
sites
in
AKR
ADH.
Employing
two
bioorthogonal
counterparts
azide–alkyne
cycloaddition
immobilization
ADH
enabled
sequential
dual‐enzyme
coating
porous
microspheres.
ordered
reactor
subsequently
used
synthesize
(
S
)‐1‐(2‐chlorophenyl)ethanol
asymmetrically
from
corresponding
prochiral
ketone,
enabling
situ
regeneration
NADPH.
exhibited
a
high
catalytic
conversion
74
%
good
reproducibility,
retaining
80
its
initial
activity
after
six
cycles.
product
had
99.9
ee,
which
that
maintained
each
cycle.
Additionally,
double‐layer
method
significantly
increased
enzyme
loading
capacity,
approximately
1.7
times
greater
than
traditional
single‐layer
immobilization.
More
importantly,
it
simultaneously
both
purification
carriers,
thus
providing
convenient
approach
facilitate
cascade
biocatalysis.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
146(1), P. 858 - 867
Published: Dec. 30, 2023
Recombinant
enzymes
have
gained
prominence
due
to
their
diverse
functionalities
and
specificity
are
often
a
greener
alternative
in
biocatalysis.
This
context
makes
purifying
recombinant
from
host
cells
other
impurities
crucial.
The
primary
goal
is
isolate
the
pure
enzyme
of
interest
ensure
its
stability
under
ambient
conditions.
Covalent
organic
frameworks
(COFs),
renowned
for
well-ordered
structure
permeability,
offer
promising
approach
histidine-tagged
(His-tagged)
enzymes.
Furthermore,
immobilizing
within
COFs
represents
growing
field
heterogeneous
In
this
study,
we
developed
flow-based
technology
utilizing
nickel-infused
covalent
framework
(Ni-TpBpy
COF)
combine
two
distinct
processes:
purification
His-tagged
immobilization
simultaneously.
Our
work
primarily
focuses
on
three
β-glucosidase,
cellobiohydrolase,
endoglucanase
as
well
proteins
with
varying
molecular
weights,
namely,
green
fluorescent
protein
(27
kDa)
BG
Rho
(88
kDa).
We
employed
Ni-TpBpy
column
matrix
showcase
versatility
our
system.
Additionally,
successfully
obtained
COF
immobilized
enzymes,
which
can
serve
catalyst
hydrolysis
p-nitrophenyl-β-d-glucopyranoside
carboxymethylcellulose.
These
demonstrated
catalytic
activity
comparable
that
free
counterparts,
added
advantages
recyclability
enhanced
conditions
an
extended
period,
ranging
60
90
days.
contrasts
do
not
maintain
effectively
over
time.
Journal of Hazardous Materials,
Journal Year:
2023,
Volume and Issue:
459, P. 132261 - 132261
Published: Aug. 9, 2023
Efficient
enzyme
immobilization
is
crucial
for
the
successful
commercialization
of
large-scale
enzymatic
water
treatment.
However,
issues
such
as
lack
high
loading
coupled
with
leaching
present
challenges
widespread
adoption
immobilized
systems.
The
study
describes
development
and
bioremediation
application
an
biocomposite
employing
a
cationic
macrocycle-based
covalent
organic
framework
(COF)
hierarchical
porosity
horseradish
peroxidase
(HRP).
intrinsic
porous
features
azacalix[4]arene-based
COF
(ACA-COF)
allowed
maximum
HRP
capacity
0.76
mg/mg
low
(<5.0
%).
biocomposite,
HRP@ACA-COF,
exhibited
exceptional
thermal
stability
(∼200
%
higher
relative
activity
than
free
enzyme),
maintained
∼60
after
five
cycles.
LCMSMS
analyses
confirmed
that
HRP@ACA-COF
system
was
able
to
achieve
>
99
degradation
seven
diverse
types
emerging
pollutants
(2-mercaptobenzothiazole,
paracetamol,
caffeic
acid,
methylparaben,
furosemide,
sulfamethoxazole,
salicylic
acid)in
under
hour.
described
enzyme-COF
offers
promise
efficient
wastewater
applications.
ACS Applied Materials & Interfaces,
Journal Year:
2024,
Volume and Issue:
16(31), P. 40371 - 40390
Published: July 29, 2024
Enzymes,
a
class
of
biocatalysts,
exhibit
remarkable
catalytic
efficiency,
specificity,
and
selectivity,
governing
many
reactions
that
are
essential
for
various
cascades
within
living
cells.
The
immobilization
structurally
flexible
enzymes
on
appropriate
supports
holds
significant
importance
in
facilitating
biomimetic
transformations
extracellular
environments.
Covalent
organic
frameworks
(COFs)
have
emerged
as
ideal
candidates
enzyme
due
to
high
surface
tunability,
diverse
chemical/structural
designs,
exceptional
stability,
metal-free
nature.
Various
techniques
been
proposed
fabricate
COF-enzyme
biocomposites,
offering
enhancements
activity
reusability
COF-immobilized
well
new
insights
into
developing
advanced
enzyme-based
applications.
In
this
review,
we
provide
comprehensive
overview
state-of-the-art
strategies
immobilizing
COFs
by
focusing
their
applicability
versatility.
These
systematically
summarized
compared
categorizing
them
postsynthesis
situ
immobilization,
where
respective
strengths
limitations
thoroughly
discussed.
Combined
with
an
critical
emerging
applications,
further
elucidate
the
multifaceted
roles
subsequent
highlighting
biofunctionality
achievable
through
COFs.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(13)
Published: Feb. 7, 2024
β-Keto-enamine-linked
2D
covalent
organic
frameworks
(COFs)
have
emerged
as
highly
robust
materials,
showing
significant
potential
for
practical
applications.
However,
the
exclusive
reliance
on
1,3,5-triformylphloroglucinol
(Tp
aldehyde)
in
design
of
such
COFs
often
results
production
non-porous
amorphous
polymers
when
combined
with
certain
amine
building
blocks.
Attempts
to
adjust
crystallinity
and
porosity
by
a
modulator
approach
are
inefficient
because
Tp
aldehyde
readily
forms
stable
β-keto-enamine-linked
monomers/oligomers
various
aromatic
amines
through
an
irreversible
keto-enol
tautomerization
process.
Our
research
employed
unique
protection-deprotection
strategy
enhance
squaramide-based
COFs.
Advanced
solid-state
NMR
studies,
including
1D
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(22)
Published: April 1, 2024
Abstract
The
design
and
orderly
layered
co‐immobilization
of
multiple
enzymes
on
resin
particles
remain
challenging.
In
this
study,
the
SpyTag/SpyCatcher
binding
pair
was
fused
to
N‐terminus
an
alcohol
dehydrogenase
(ADH)
aldo‐keto
reductase
(AKR),
respectively.
A
non‐canonical
amino
acid
(ncAA),
p
‐azido‐L‐phenylalanine
(p‐AzF),
as
anchor
for
covalent
bonding
enzymes,
genetically
inserted
into
preselected
sites
in
AKR
ADH.
Employing
two
bioorthogonal
counterparts
azide–alkyne
cycloaddition
immobilization
ADH
enabled
sequential
dual‐enzyme
coating
porous
microspheres.
ordered
reactor
subsequently
used
synthesize
(
S
)‐1‐(2‐chlorophenyl)ethanol
asymmetrically
from
corresponding
prochiral
ketone,
enabling
situ
regeneration
NADPH.
exhibited
a
high
catalytic
conversion
74
%
good
reproducibility,
retaining
80
its
initial
activity
after
six
cycles.
product
had
99.9
ee,
which
that
maintained
each
cycle.
Additionally,
double‐layer
method
significantly
increased
enzyme
loading
capacity,
approximately
1.7
times
greater
than
traditional
single‐layer
immobilization.
More
importantly,
it
simultaneously
both
purification
carriers,
thus
providing
convenient
approach
facilitate
cascade
biocatalysis.
Advanced Science,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 28, 2024
Abstract
Metal–organic
frameworks
(MOFs)
and
covalent–organic
(COFs)‐based
aerogels
are
garnering
significant
attention
owing
to
their
unique
chemical
structural
properties.
These
materials
harmoniously
combine
the
advantages
of
MOFs
COFs—such
as
high
surface
area,
customizable
porosity,
varied
functionality—with
lightweight
structured
porosity
characteristic
aerogels.
This
combination
opens
up
new
avenues
for
advanced
applications
in
fields
where
material
efficiency
enhanced
functionality
critical.
review
provides
a
comparative
overview
synthetic
strategies
utilized
produce
pristine
MOF/COF
well
MOF/COF‐based
hybrid
aerogels,
which
functionalized
with
molecular
precursors
nanoscale
materials.
The
versatility
these
positions
them
promising
candidates
addressing
complex
challenges
environmental
remediation,
energy
storage
conversion,
sustainable
water‐energy
technologies,
separations.
Furthermore,
this
study
discusses
current
future
prospects
related
synthesis
techniques
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: Jan. 24, 2025
Two
or
more
catalysts
conducting
multistep
reactions
in
the
same
reactor,
concurrent
tandem
catalysis,
could
enable
(bio)pharmaceutical
and
fine
chemical
manufacturing
to
become
much
sustainable.
Herein
we
report
that
co-immobilization
of
metal
nanoparticles
a
biocatalytic
system
within
synthetic
covalent
organic
framework
capsule,
COFcap-2,
functions
like
an
artificial
cell
that,
whereas
are
trapped
300-400
nm
cavities,
substrates/products
can
ingress/egress
through
ca.
2
windows.
The
COFcap-2
reactor
is
first
coated
onto
electrode
surface
then
used
prepare
eleven
homochiral
amines
using
dinitrogen
as
feedstock.
amines,
including
drug
product
intermediates
active
pharmaceutical
ingredient,
prepared
>99%
enantiomeric
excess
under
ambient
conditions
water.
Importantly,
recycled
15
times
with
retention
performance,
addressing
relative
instability
poor
recyclability
enzymes
has
hindered
their
broad
implementation
for
energy-efficient,
low
waste
production
chemicals
(bio)pharmaceuticals.
Concurrent
two
would
be
beneficial
manufacturing.
Here,
authors
multienzyme
employ
it
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(8)
Published: Nov. 21, 2023
Nanomedicines
are
extensively
used
in
cancer
therapy.
Covalent
organic
frameworks
(COFs)
crystalline
porous
materials
with
several
benefits
for
therapy,
including
porosity,
design
flexibility,
functionalizability,
and
biocompatibility.
This
review
examines
the
use
of
COFs
therapy
from
perspective
reticular
chemistry
function-oriented
design.
First,
modification
sites
functionalization
methods
discussed,
followed
by
their
potential
as
multifunctional
nanoplatforms
tumor
targeting,
imaging,
integrating
functional
components.
Finally,
some
challenges
clinical
translation
presented
hope
promoting
development
COF-based
anticancer
nanomedicines
bringing
closer
to
trials.
Chemistry of Materials,
Journal Year:
2024,
Volume and Issue:
36(2), P. 959 - 967
Published: Jan. 5, 2024
Covalent
organic
frameworks
(COFs)
are
an
emerging
class
of
two-dimensional
(2D)
or
three-dimensional
(3D)
porous
structures.
Most
COFs
typically
prepared
via
solvothermal
methods
involving
long
reaction
times
(>12
h)
that
generally
result
in
unprocessable
powders,
significantly
hindering
their
straightforward
integration
into
devices
and
applications.
Current
processing
for
2D
have
not
been
implemented
3D
COFs,
probably
due
to
the
lack
preassembly
mechanisms
among
COF
precursors
during
synthesis.
Here,
we
report
a
pioneering
synthetic
environment
achieves
two
objectives:
precise
control
over
time
through
controlled
diffusion,
ensuring
absence
turbulent
mixing,
ability
fine-tune
specific
zone
where
diffusion
will
occur.
We
further
demonstrate
controlling
these
features
creates
unparalleled
environment,
allowing
rapid
one-pot
synthesis
with
formation
occurring
less
than
minute.
Additionally,
this
approach
yields
self-standing
fibers
on
centimeter
scale,
showcasing
versatility
potential
presented
scalable
production
as
well
seamless
patterning
strategies.
