Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(48)
Published: Oct. 5, 2023
Abstract
Polymerization‐induced
self‐assembly
(PISA)
is
a
powerful
technique
for
preparing
block
copolymer
nanostructures.
Recently,
efforts
have
been
focused
on
applying
photochemistry
to
promote
PISA
due
the
mild
reaction
conditions,
low
cost,
and
spatiotemporal
control
that
light
confers.
Despite
these
advantages,
chain‐end
degradation
long
times
can
mar
efficacy
of
this
process.
Herein,
we
demonstrate
use
ultrafast
photoiniferter
produce
polymeric
By
exploiting
rapid
photolysis
xanthates,
near‐quantitative
monomer
conversion
be
achieved
within
five
minutes
prepare
micelles,
worms,
vesicles
at
various
core‐chain
lengths,
concentrations,
or
molar
compositions.
Macromolecular Rapid Communications,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Aug. 5, 2024
In
recent
years,
the
fully
oxygen-tolerant
reversible
deactivation
radical
polymerization
(RDRP)
has
become
a
highly
researched
area.
this
contribution,
new
and
minimalist
method
is
successfully
employed
to
accomplish
addition-fragmentation
chain
transfer
(RAFT)
using
bis(trithiocarbonate)
disulfides
(BisTTC)
as
an
iniferter
agent,
where
released
sulfur-centered
trithiocarbonate
(TTC)
can
initiate
monomer.
Furthermore,
kinetics
revealed
typical
"living"
features
of
system.
More
importantly,
by
high-throughput
screening,
it
found
that
dodecyl-substituted
TTC
responsible
for
RAFT
though
initiation
R
deoxygenation.
It
believed
strategy
provides
powerful
tool
RDRPs.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 26, 2024
Abstract
We
report
a
conceptually
new
amplified
cascade
catalysis
that
converts
oxygen
to
hydroxyl
radical
for
controlled
RAFT
polymerization.
This
consists
of
two
sequential
reactions,
deoxygenation
catalyzed
by
glucose
oxidase
and
Fenton
reaction
ferrocene.
The
catalysts
can
communicate
with
each
other,
leading
ferrocene
recycling
hence
amplification
in
generation.
Ferrocene
was
confirmed
UV/Vis
spectroscopy,
molecular
docking
simulation,
electron
paramagnetic
resonance
as
well
polymerization
studies.
applied
various
monomers,
yielding
well‐defined
homopolymers
diblock
copolymers
weights
low
dispersities.
Poly(
N
,
‐dimethyl
acrylamide)
weight
over
1
million
g
mol
−1
also
successfully
synthesized
under
ambient
conditions.
Ferrocene‐functionalized
microspheres
were
prepared
used
recyclable
catalyst
five
consecutive
polymerizations
minimal
declination
monomer
conversion,
which
further
improved
the
ecofriendly
character
this
methodology.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 26, 2024
We
report
a
conceptually
new
amplified
cascade
catalysis
that
converts
oxygen
to
hydroxyl
radical
for
controlled
RAFT
polymerization.
This
consists
of
two
sequential
reactions,
deoxygenation
catalyzed
by
glucose
oxidase
and
Fenton
reaction
ferrocene.
The
catalysts
can
communicate
with
each
other,
leading
ferrocene
recycling
hence
amplification
in
generation.
Ferrocene
was
confirmed
UV/Vis
spectroscopy,
molecular
docking
simulation,
electron
paramagnetic
resonance
as
well
polymerization
studies.
applied
various
monomers,
yielding
well-defined
homopolymers
diblock
copolymers
weights
low
dispersities.
Poly(N,N-dimethyl
acrylamide)
weight
over
1
million
g
mol
Polymers,
Journal Year:
2024,
Volume and Issue:
16(24), P. 3493 - 3493
Published: Dec. 14, 2024
Anionic
thermo-
and
pH-responsive
copolymers
were
synthesized
by
photoiniferter
reversible
addition–fragmentation
chain
transfer
polymerization
(PI-RAFT).
The
thermo-responsive
properties
provided
oligo(ethylene
glycol)-based
macromonomer
units
containing
hydrophilic
hydrophobic
moieties.
enabled
the
addition
of
5–20
mol%
strong
(2-acrylamido-2-methylpropanesulfonic)
weak
(methacrylic)
acids.
Upon
initiation
visible
light
at
470
nm
in
absence
radical
initiators,
yields
from
ternary
reached
94%
2.5
h
when
process
was
carried
out
continuous
flow
mode
using
4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic
acid
as
a
light-sensitive
RAFT
agent.
polymers
characterized
size
exclusion
chromatography,
IR
NMR
spectroscopy,
differential
scanning
calorimetry.
featured
sufficiently
high
molecular
weight
(93–146
kDa)
consistent
with
theoretical
values
satisfactory
dispersities
range
1.18–1.45.
studied
deionized
water,
saline,
buffer
solutions.
Dramatic
differences
LCST
behavior
observed
acid-based
polyelectrolytes.
introduction
sulfonic
units,
even
very
small
amounts,
completely
suppressed
transition
water
while
maintaining
it
saline
solutions,
negligible
dependence
on
pH.
In
contrast,
incorporation
methacrylic
demonstrated
pronounced
pH
dependence.
peculiarities
micelle
formation
aqueous
solutions
investigated
critical
concentrations
their
ability
to
retain
pyrene,
drug
model,
determined.
It
that
anionic
brushes
formed
micelles
aggregation
numbers
1–2
order
10−4
mg/mL.
These
have
entrap
which
makes
them
promising
tool
for
targeted
delivery.
Advanced Functional Materials,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 2, 2024
Abstract
Metal‐organic
frameworks
bearing
coordinatively
unsaturated
metal
sites
(CUSs)
exhibit
distinctive
interactions
toward
guest
molecules,
thereby
presenting
intriguing
properties
in
photocatalytic
applications.
Herein,
an
adaptable
strategy
is
established
to
create
2D
metal‐porphyrin
while
engineering
the
CUSs
based
on
use
of
bivalent
nodes
(Zn
2+
,
Co
Cu
Ni
Cd
)
and
Zr‐O
clusters.
The
strong
surface‐coordination
effect
reduces
energy
barriers
activate
acrylate
monomers
adsorbed
nanosheet
frameworks,
enabling
generation
anion
radicals
through
a
broadband
light‐induced
electron
transfer
pathway.
Particularly,
cycle
offers
hole‐mediated
deactivation
mechanism
regulate
radical
concentrations
polymerization
system,
propagating
chains
surface‐confined
growth
behavior
that
significantly
inhibits
recombination
terminations.
Extensive
mechanistic
studies
theoretical
calculations
reveal
molecular‐level
guest‐framework
establish
guidelines
screen
centers
for
fabricating
valid
photocatalysts
compatible
with
photo‐regulated
polymerization.
A
series
ultrahigh
molecular
weight
polymers
M
n
>
1
000
relatively
low
dispersity
(
Đ
≈
1.5)
are
obtained
upon
exposure
full
spectrum
visible
light.
This
study
provides
novel
inspirations
harnessing
natural
sunlight
drive
macromolecular
synthesis
minimal
consumption.
Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(48)
Published: Oct. 5, 2023
Abstract
Polymerization‐induced
self‐assembly
(PISA)
is
a
powerful
technique
for
preparing
block
copolymer
nanostructures.
Recently,
efforts
have
been
focused
on
applying
photochemistry
to
promote
PISA
due
the
mild
reaction
conditions,
low
cost,
and
spatiotemporal
control
that
light
confers.
Despite
these
advantages,
chain‐end
degradation
long
times
can
mar
efficacy
of
this
process.
Herein,
we
demonstrate
use
ultrafast
photoiniferter
produce
polymeric
By
exploiting
rapid
photolysis
xanthates,
near‐quantitative
monomer
conversion
be
achieved
within
five
minutes
prepare
micelles,
worms,
vesicles
at
various
core‐chain
lengths,
concentrations,
or
molar
compositions.
