Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(26)
Published: April 16, 2024
Abstract
To
develop
new
hybrid
micelles
with
alkyl/polyaromatic
core–shell
structures,
we
synthesized
umbrella‐shaped
amphiphiles
bearing
a
bent
anthracene
dimer
linear
alkyl
chain
(i.e.,
octyl
and
hexadecyl
groups).
The
quantitatively
assemble
into
spherical
(~2–3
nm
in
core
diameter),
possessing
an
alkylated
cavity
surrounded
by
polyaromatic
framework,
water.
alkylation
significantly
enhances
the
stability
of
micellar
structures
against
dilution
(up
to
9
μM)
heat
>120
°C).
highly
condensed
micelle,
as
indicated
solvatochromic
guest
probes,
displays
increased
uptake
ability
toward
large
metallodyes.
Interestingly,
efficient
aromatic
macrocycles
[
n
]cycloparaphenylenes)
present
micelle
provides
pseudorotaxane‐shaped
host–guest
composites
high
emissivity
(
Φ
F
=up
35
%).
Internal
multi‐alkylation
can
thus
successfully
enhance
its
assembly
stability/guest
functions.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(26), P. 17887 - 17897
Published: June 24, 2024
Amide-based
organic
cage
cavities
are,
in
principle,
ideal
enzyme
active
site
mimics.
Yet,
cage-promoted
organocatalysis
has
remained
elusive,
large
part
due
to
synthetic
accessibility
of
robust
and
functional
scaffolds.
Herein,
we
report
the
acyl
transfer
catalysis
properties
robust,
hexaamide
cages
solvent.
Cage
structural
variation
reveals
that
esterification
with
an
anhydride
carrier
occurs
only
bifunctional
featuring
internal
pyridine
motifs
two
crucial
antipodal
carboxylic
acid
groups.
1H
NMR
data
X-ray
crystallography
show
is
rapidly
activated
inside
cavity
as
a
covalent
mixed-anhydride
intermediate
hydrogen
bond.
Michaelis–Menten
(saturation)
kinetics
suggest
weak
binding
(KM
=
0.16
M)
alcohol
pronucleophile
close
anhydride.
Finally,
activation
delivery
by
second
group
forms
ester
product
releases
catalyst.
Eyring
analysis
indicates
strong
enthalpic
stabilization
transition
state
(5.5
kcal/mol)
corresponding
rate
acceleration
104
over
background
acylation,
ordered,
associative
rate-determining
attack
alcohol,
supported
DFT
calculations.
We
conclude
specific
design
responsible
for
enhancement
reaction.
These
results
pave
way
organic-phase
mimicry
self-assembled
potential
elaboration
enact
selective
acylations.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(17), P. 6536 - 6543
Published: Jan. 1, 2024
Integrating
symmetry-reducing
methods
into
self-assembly
methodology
is
desirable
to
efficiently
realise
the
full
potential
of
molecular
cages
as
hosts
and
catalysts.
Although
techniques
have
been
explored
for
metal
organic
(coordination)
cages,
rational
strategies
develop
low
symmetry
remain
limited.
In
this
article,
we
describe
rules
program
shape
cage
cavities
by
designing
edge
pieces
that
bias
orientation
amide
linkages.
We
apply
synthesise
with
well-defined
cavities,
supported
evidence
from
crystallography,
spectroscopy
modelling.
Access
low-symmetry,
self-assembled
such
those
presented,
will
widen
current
bottleneck
preventing
study
enzyme
mimics,
provide
synthetic
tools
novel
functional
material
design.
Molecules,
Journal Year:
2025,
Volume and Issue:
30(3), P. 462 - 462
Published: Jan. 21, 2025
Metal–organic
cages
(MOCs)
are
discrete
supramolecular
entities
consisting
of
metal
nodes
and
organic
connectors
or
linkers;
MOCs
noted
for
their
high
porosity
processability.
Chemically,
they
can
be
post-synthetically
modified
(PSM)
new
functional
groups
introduced,
presenting
attractive
qualities,
it
is
expected
that
properties
will
differ
from
those
the
original
compound.
This
why
highly
regarded
in
fields
biology
chemistry.
The
present
review
deals
with
current
PSM
strategies
used
MOCs,
including
covalent,
coordination,
noncovalent
methods
structural
benefits.
main
emphasis
this
to
show
what
extent
under
circumstances
a
MOC
designed
obtain
tailored
geometric
architecture.
Although
sometimes
unclear
when
examining
systems,
particularizing
design
systematic
approaches
development
characterization
families
provides
insights
into
structure–function
relationships,
which
guide
future
developments.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(23)
Published: April 5, 2024
Abstract
A
dinuclear
metal‐organic
cage
with
four
acrylate
side
chains
was
prepared
by
self‐assembly.
Precipitation
polymerization
of
the
N‐isopropylacrylamide
yielded
a
thermoresponsive
nanogel.
The
host
properties
were
retained
within
gel
matrix,
endowing
nanogel
capability
to
serve
as
sorbent
for
chloride
ions
in
water.
Moreover,
heteroleptic
drug
abiraterone
co‐ligand
integrated
into
addition
induced
structural
rearrangement
metal‐ligand
assembly,
resulting
gradual
release
abiraterone.
Beilstein Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
21, P. 421 - 443
Published: Feb. 24, 2025
The
bespoke
environments
in
enzyme
active
sites
can
selectively
accelerate
chemical
reactions
by
as
much
1019.
Macromolecular
and
supramolecular
chemists
have
been
inspired
to
understand
mimic
these
accelerations
selectivities
for
applications
catalysis
sustainable
synthesis.
Over
the
past
60+
years,
mimicry
strategies
evolved
with
changing
interests,
understanding,
synthetic
advances
but,
ubiquitously,
research
has
focused
on
use
of
a
molecular
"cavity".
activities
different
cavities
vary
subset
features
available
particular
cavity
type.
Unsurprisingly,
without
access
mimics
able
encompass
more/all
functional
sites,
examples
cavity-catalyzed
processes
demonstrating
enzyme-like
rate
remain
rare.
This
perspective
will
briefly
highlight
some
key
traditional
catalysis,
type,
order
contextualize
recent
development
robust
organic
cage
catalysts,
which
exploit
stability,
functionality,
reduced
symmetry
enable
promising
catalytic
modes.
Chemical Science,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
Hydrogels
with
Pd
n
L
2
-type
junctions
can
be
obtained
by
photoinitiated
copolymerization
of
palladium
cages
acrylamide
monomers
in
water.
The
dynamic
nature
the
cage
crosslinks
allows
for
an
anion-induced
switch
network
topology.
A
chiral
endohedral
Pd12Ala24
metal–organic
cage
(MOC)
incorporating
enantiomeric
tert-butyloxycarbonylalanine
(Boc-Ala)
ligands
is
synthesized
as
a
model
system
of
macrocation
containing
internal
centers
away
from
the
surface
MOC.
The
geometry
leads
to
interaction
between
these
inside
MOCs
far
other
components
such
counterions
in
solution.
consequence
that
recognition
(two
MOC
enantiomers
self-assemble
individually
their
mixed
solution)
and
discrimination
(self-assembly
favors
one
enantiomer
over
other)
previously
observed
self-assembly
carrying
exohedral
become
weaker
or
completely
disappear
current
solutions,
demonstrating
effective
electrostatic
short
range
critical
for
behavior
macromolecules
during
self-assembly.
Different
small
species
solution
(e.g.,
arabinose,
lactate,
tartrate,
γ-cyclodextrin)
show
various
capabilities
on
self-assembly,
based
size
charge
species.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(26)
Published: April 16, 2024
Abstract
To
develop
new
hybrid
micelles
with
alkyl/polyaromatic
core–shell
structures,
we
synthesized
umbrella‐shaped
amphiphiles
bearing
a
bent
anthracene
dimer
linear
alkyl
chain
(i.e.,
octyl
and
hexadecyl
groups).
The
quantitatively
assemble
into
spherical
(~2–3
nm
in
core
diameter),
possessing
an
alkylated
cavity
surrounded
by
polyaromatic
framework,
water.
alkylation
significantly
enhances
the
stability
of
micellar
structures
against
dilution
(up
to
9
μM)
heat
>120
°C).
highly
condensed
micelle,
as
indicated
solvatochromic
guest
probes,
displays
increased
uptake
ability
toward
large
metallodyes.
Interestingly,
efficient
aromatic
macrocycles
[
n
]cycloparaphenylenes)
present
micelle
provides
pseudorotaxane‐shaped
host–guest
composites
high
emissivity
(
Φ
F
=up
35
%).
Internal
multi‐alkylation
can
thus
successfully
enhance
its
assembly
stability/guest
functions.
ChemPlusChem,
Journal Year:
2023,
Volume and Issue:
88(7)
Published: July 1, 2023
Abstract
The
recognition
of
carbohydrate
plays
a
key
role
in
numerous
biological
processes.
Thus,
artificial
receptors
have
been
synthesized
to
mimic
these
systems.
To
date,
most
the
reported
for
complexation
present
highly
symmetrical
cavities,
probably
because
their
syntheses
require
less
synthetic
efforts
and
are
easier
achieve
control.
However,
carbohydrates
display
complex,
asymmetrical
structures
suggesting
that
hosts
with
low
symmetry
might
be
more
adapted
recognize
guests.
Here,
we
described
strategies
used
complex
macrocycles
cages
presenting
potential
this
approach.
Self‐assembled
first
described,
then
covalent
presented
each
example
binding
properties
low‐symmetry
systems
compared
those
higher‐symmetry
counterparts.
