Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 6, 2024
Abstract
An
enzyme‐mimicking
catalytic
system
has
been
established
using
a
singular
palladium‐based
octahedral
cage
as
the
supramolecular
reactor,
deftly
unlocking
off‐on‐off
selectivity
in
semi‐hydrogenation
of
alkynes.
Water
serves
critical
regulator,
modulating
catalyst
states,
reaction
rates,
and
endpoints.
The
choice
solvent
influences
activity
host–guest
binding
types
homogeneous
heterogeneous
catalysis,
effectively
modifying
steps
involved
Z
→
E
isomerization
during
Kinetic
inhibition
experiments
indicate
that
mimics
activation
characteristics
enzymes
towards
substrates,
enabling
selective
transformations
within
confined
environment.
utility
this
switchable
cage‐confined
catalysis
demonstrated
synthesis
modification
complex
biologically
active
molecules
with
controllable
/
selectivity.
This
work
sheds
light
on
design
control
artificial
counterparts
enzymes,
offering
fundamental
insights
into
factors
influencing
biological
macromolecules.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(23), С. 15787 - 15795
Опубликована: Май 13, 2024
The
encapsulation
of
different
guest
molecules
by
their
recognition
domains
proteins
leads
to
selective
binding,
catalysis,
and
transportation.
Synthetic
hosts
capable
selectively
binding
guests
in
cavities
mimic
the
function
are
highly
desirable
but
challenging.
Here,
we
report
three
ladder-shaped,
triple-cavity
metallacages
prepared
multicomponent
coordination-driven
self-assembly.
Interestingly,
porphyrin-based
metallacage
is
heteroleptic
fullerenes
(C60
or
C70)
coronene
using
its
cavities,
allowing
distinct
allosteric
upon
addition
C60
C70.
Owing
affinities
one
molecule
central
cavity
two
units
side
while
encapsulating
C70
cavity.
rational
design
multicavity
assemblies
that
enable
will
guide
further
advanced
supramolecular
constructs
with
tunable
properties.
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 12, 2025
Coordination
cages
with
specific
properties
and
functionalities
are
utilized
as
reaction
vessels
for
the
desired
chemical
transformation
of
substrates.
The
symmetry
inherent
cavity
coordination
can
influence
host–guest
interactions
outcome
in
their
confined
space.
However,
impact
cage
shape
on
different
transformations
remains
unclear.
In
this
chapter,
we
report
chemo-selective
anthracene
derivative
using
three
geometrically
distinct
Pd6
(CC2,
CC3,
CC4).
Photoirradiation
9-bromoanthracene
(G3)
distorted
double-square
(CC2)
yields
anthracene-9,10-dione,
while
known
(CC3)
forms
a
[4
+
4]
cycloaddition
product.
same
bowl-shaped
(CC4)
resulted
oxidized
Through
combination
experimental
computational
studies,
demonstrate
that
size
significantly
pathways
encapsulated
derivative,
leading
to
chemo-selectivity.
Furthermore,
observe
encapsulation
cavities
(CC2
CC4)
leads
significant
enhancement
rate
photooxidation
G3.
This
work
underscores
versatility
water-soluble
synthetic
chemistry,
offering
interesting
avenues
transformation.
The
conversion
of
toluene
into
high-value
products
without
generating
undesired
CO2
remains
a
critical
challenge.
Selective
oxidation
under
visible
light
irradiation
has
emerged
as
promising
solution.
This
review
offers
comprehensive
interpretation
photocatalytic
transformations
in
heterogeneous
oxidation.
We
start
by
outlining
the
basic
mechanism
C–H
bond
activation
and
provide
an
overview
reactive
oxygen
species
(ROS)
within
systems.
Subsequently,
we
summary
strategies
that
have
been
developed
to
enhance
selectivity
system.
Following
this,
advanced
characterization
techniques
density
functional
theory
(DFT)
calculations
are
discussed
for
understanding
structure-performance
relationship
photocatalysts
mechanisms
underlying
processes.
Finally,
put
forward
detailed
discussion
current
challenges
potential
directions
future
research,
with
aim
offering
valuable
insights
this
emerging
field.
believe
will
not
only
spark
greater
creativity
optimizing
but
also
offer
designing
other
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 11, 2025
The
electrocatalytic
oxidation
of
benzyl
alcohol
to
benzoic
acid
is
a
process
that
often
requires
high
voltage,
leading
increased
energy
consumption,
side
reactions
(oxygen
evolution
reaction
(OER)),
and
catalyst
degradation.
Herein,
our
study
introduces
novel
approach.
We
demonstrate
PtZn-ZnOx
featuring
PtZn
intermetallic
structure
with
abundant
interfaces
on
the
surface
allows
for
an
impressive
selectivity
99.5%
at
low
potential
0.725
V
(vs
reversible
hydrogen
electrode,
RHE),
which
0.6
lower
than
most
reported
studies.
This
testament
efficiency
catalyst,
as
it
significantly
reduces
occurrence
reactions,
more
efficient
sustainable
process.
experimental
density
functional
theory
calculations
demonstrated
adsorption
Ph–CH2OH
Ph–CHO
generation
electrophilic
OH*
were
promoted
due
unsaturated
coordination
Zn
atom
in
interfaces.
Furthermore,
potential-determining
step
coupling
was
barrier
interface,
improved
catalytic
activity
selectivity.
outlines
approach
designing
highly
electrocatalysts
high-efficiency
valorization
voltages.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(43)
Опубликована: Май 29, 2024
Abstract
Metal‐organic
frameworks
(MOFs)
and
metal‐organic
cages
(MOCs)
have
garnered
significant
attention
as
promising
photocatalysts
due
to
their
tunable
chemical
structures
integrated
multifunctionality.
To
increase
the
photocatalytic
efficiency,
strategies
like
ligand
functionalization,
introducing
additional
catalytic
sites,
doping
or
encapsulating
photosensitizers
been
explored
for
both
MOFs
MOCs.
This
concept
review
focuses
on
recent
advancements
in
utilizing
MOCs
hydrogen
production,
highlighting
unique
characteristics
respective
mechanisms
this
field.
Moreover,
it
outlines
current
challenges
prospects
faced
by
MOCs,
offering
an
outlook
future
domain.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(45), С. 30933 - 30946
Опубликована: Окт. 21, 2024
Flavin
adenine
dinucleotide
(FAD),
serving
as
a
light-absorbing
coenzyme
factor,
can
undergo
conformationally
isomeric
complexation
within
different
enzymes
to
form
various
enzyme-coenzyme
complexes,
which
exhibit
photocatalytic
functions
that
play
crucial
role
in
physiological
processes.
Constructing
an
artificial
photofunctional
system
using
FAD
or
its
derivatives
not
only
develop
biocompatible
systems
with
excellent
activities
but
also
further
enhance
our
understanding
of
the
biological
systems.
Here,
we
demonstrate
supramolecular
approach
for
constructing
enzyme-coenzyme-type
host-guest
complex
photoinduced
catalytic
function
water.
First,
have
designed
and
synthesized
water-soluble
tetraphenylethene
(TPE)-based
octacationic
molecular
cage
(
Chemical Science,
Год журнала:
2024,
Номер
15(23), С. 8913 - 8921
Опубликована: Янв. 1, 2024
The
construction
and
application
of
metal-organic
cages
with
accessible
internal
cavities
have
witnessed
rapid
development,
however,
the
precise
synthesis
complex
capsules
multiple
achievement
multi-guest
encapsulation,
further
in-depth
comprehension
host-multi-guest
recognition
remain
a
great
challenge.
Just
like
building
LEGO
blocks,
herein,
we
constructed
series
high-order
layered
architectures
generation
n
(n
=
1/2/3/4
is
also
number
cavities)
by
multi-component
coordination-driven
self-assembly
using
porphyrin-containing
tetrapodal
ligands
(like
plates),
parallel-podal
clamps)
metal
ions
nodes).
Importantly,
these
assembled
structures
possessed
different
numbers
rigid
separate
formed
overlapped
porphyrin
planes
specific
gaps.
host-guest
experiments
convincing
characterization
proved
that
G2-G4
could
serve
as
host
to
achieve
unprecedentedly
encapsulate
up
four
C60
molecules.
More
interestingly,
revealed
negative
cooperation
behavior
in
process
recognition,
which
provides
new
platform
study
complicated
interaction
field
supramolecular
chemistry.
Metal–organic
cycles/cages
(MOCs)
are
a
class
of
nanoscale
molecular
entities
that
possess
distinct
shapes
and
sizes
designed
synthesized
through
the
predictable
integration
organic
inorganic
ligands.
The
diverse
functionalities
MOCs
render
them
valuable
in
fields
biology,
chemistry,
materials.
First,
cavity
renders
suitable
for
host–guest
interactions,
which
subsequently
employed
to
induce
conformational
changes,
this
approach
is
particularly
advantageous
catalysis,
sensing,
controlled
loading
release.
Furthermore,
MOC-
polymer-based
aggregates
can
be
applied
biomedical
research
cascaded
light-harvesting
systems.
Benefiting
from
high
specific
surface
area,
initial
exploration
MOC-based
hierarchical
assemblies
indicates
their
potential
applications
biomedicine
catalysis.
microsheets
centimeter
films
used
dual-mode
catalysis
novel
wound
dressing
nonhealing
wounds.
In
addition,
design
synthesis
with
different
various
strategies
discussed.
We
summarized
latest
progress
past
5
years
Review.