ACS Macro Letters,
Journal Year:
2022,
Volume and Issue:
12(1), P. 14 - 19
Published: Dec. 19, 2022
We
report
on
a
fundamental
feature
of
photoiniferter
polymerizations
mediated
with
trithiocarbonates
and
xanthates.
The
were
found
to
be
highly
dependent
the
activated
electronic
excitation
iniferter.
Enhanced
rates
polymerization
greater
control
over
molecular
weights
observed
for
trithiocarbonate-
xanthate-mediated
when
n
→
π*
transition
iniferter
was
targeted
compared
activating
π
transition.
disparities
in
attributed
increased
rate
C–S
photolysis
which
confirmed
using
model
trapping
studies.
This
study
provides
valuable
insight
into
role
excitations
guidance
selecting
irradiation
conditions
applications
where
light
sensitivity
is
important.
Chemical Society Reviews,
Journal Year:
2023,
Volume and Issue:
52(9), P. 3035 - 3097
Published: Jan. 1, 2023
In
this
review,
we
provide
a
brief
history,
progress,
and
applications,
discuss
the
remaining
challenges
of
photocontrolled
reversible
addition-fragmentation
chain
transfer
(RAFT)
polymerization
(i.e.,
photoinduced
electron/energy
transfer-RAFT
(PET-RAFT),
photoiniferter,
photomediated
cationic
RAFT
polymerization).
Among
these,
visible-light-driven
has
attracted
particular
attention
in
recent
years
due
to
its
benefits,
including
low
energy
consumption
safe
reaction
procedure.
Moreover,
incorporation
visible-light
photocatalysis
conferred
attractive
features,
such
as
spatiotemporal
control
oxygen
tolerance;
however,
clear
understanding
mechanism
not
been
completely
provided.
We
also
present
research
efforts
elucidate
mechanisms
with
aid
quantum
chemical
calculations
combined
experimental
evidence.
This
review
offers
an
insight
into
better
design
systems
for
desired
applications
helps
realize
full
potential
both
academic-
industrial-scale
applications.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(44), P. 24315 - 24327
Published: Oct. 25, 2023
Photoinduced
reversible-deactivation
radical
polymerization
(photo-RDRP)
techniques
offer
exceptional
control
over
polymerization,
providing
access
to
well-defined
polymers
and
hybrid
materials
with
complex
architectures.
However,
most
photo-RDRP
methods
rely
on
UV/visible
light
or
photoredox
catalysts
(PCs),
which
require
multistep
synthesis.
Herein,
we
present
the
first
example
of
fully
oxygen-tolerant
red/NIR-light-mediated
photoinduced
atom
transfer
(photo-ATRP)
in
a
high-throughput
manner
under
biologically
relevant
conditions.
The
method
uses
commercially
available
methylene
blue
(MB+)
as
PC
[X-CuII/TPMA]+
(TPMA
=
tris(2-pyridylmethyl)amine)
deactivator.
mechanistic
study
revealed
that
MB+
undergoes
reductive
quenching
cycle
presence
TPMA
ligand
used
excess.
formed
semireduced
MB
(MB•)
sustains
by
regenerating
[CuI/TPMA]+
activator
together
provides
polymerization.
This
dual
catalytic
system
exhibited
excellent
oxygen
tolerance,
enabling
polymerizations
high
monomer
conversions
(>90%)
less
than
60
min
at
low
volumes
(50-250
μL)
synthesis
library
DNA-polymer
bioconjugates
narrow
molecular
weight
distributions
(Đ
<
1.30)
an
open-air
96-well
plate.
In
addition,
broad
absorption
spectrum
allowed
ATRP
be
triggered
UV
NIR
irradiation
(395-730
nm).
opens
avenues
for
integration
orthogonal
reactions.
Finally,
MB+/Cu
catalysis
showed
good
biocompatibility
during
cells,
expands
potential
applications
this
method.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(10)
Published: Jan. 16, 2023
Hyperbranched
polymethacrylates
were
synthesized
by
green-light-induced
atom
transfer
radical
polymerization
(ATRP)
under
biologically
relevant
conditions
in
the
open
air.
Sodium
2-bromoacrylate
(SBA)
was
prepared
situ
from
commercially
available
2-bromoacrylic
acid
and
used
as
a
water-soluble
inibramer
to
induce
branching
during
copolymerization
of
methacrylate
monomers.
As
result,
well-defined
branched
obtained
less
than
30
min
with
predetermined
molecular
weights
(36
000
European Polymer Journal,
Journal Year:
2024,
Volume and Issue:
211, P. 113001 - 113001
Published: March 30, 2024
Atom
transfer
radical
polymerization
(ATRP)
is
one
of
the
most
often
used
controlled
techniques.
It
employs
very
small
amounts
(ppm)
Cu
complexes
in
presence
various
chemical
reducing
agents
but
also
external
stimuli
such
as
light,
electrical
current
or
mechanical
forces.
can
be
carried
out
bulk,
solution,
and
dispersed
media.
ATRP
has
been
successfully
to
prepare
polymers
with
architecture
well-defined
topology,
composition,
functionality,
well
bioconjugates
organic–inorganic
hybrids.
This
article
summarizes
status
an
outlook
for
ATRP.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(19), P. 13417 - 13426
Published: May 1, 2024
Photoinduced
polymerization
techniques
have
gathered
significant
attention
due
to
their
mild
conditions,
spatiotemporal
control,
and
simple
setup.
In
addition
homogeneous
media,
efforts
been
made
implement
photopolymerization
in
emulsions
as
a
practical
greener
process.
However,
previous
photoinduced
reversible
deactivation
radical
(RDRP)
heterogeneous
media
has
relied
on
short-wavelength
lights,
which
limited
penetration
depth,
resulting
slow
relatively
poor
control.
this
study,
we
demonstrate
the
first
example
of
highly
efficient
miniemulsion
ATRP
open
air
driven
by
red
or
near-infrared
(NIR)
light.
This
was
facilitated
utilization
water-soluble
photocatalyst,
methylene
blue
(MB+).
Irradiation
red/NIR
light
allowed
for
excitation
MB+
subsequent
photoreduction
deactivator
presence
electron
donors
initiate
mediate
The
NIR
light-driven
photoATRP
provided
successful
synthesis
polymers
with
low
dispersity
(1.09
≤
Đ
1.29)
quantitative
conversion
within
an
hour.
study
further
explored
impact
kinetics
reactors
varying
sizes
large-scale
reaction
(250
mL),
highlighting
advantages
longer-wavelength
light,
particularly
dispersed
owing
its
superior
penetration.
work
opens
new
avenues
robust
emulsion
techniques,
offering
more
approach
improved
control
efficiency.
Chemical Communications,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
This
article
highlights
the
advancements
in
controlled
radical
polymerization
facilitated
by
three
external
regulations
of
oxygen,
light,
and
mechanical
force,
outlines
future
directions
polymerization.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 16, 2025
In
traditional
atom
transfer
radical
polymerization
(ATRP),
oxygen
must
be
meticulously
eliminated
due
to
its
propensity
quench
species
and
halt
the
process.
Additionally,
oxidizes
lower-valent
Cu
catalyst,
compromising
ability
activate
alkyl
halides
propagate
polymerization.
this
study,
we
present
an
oxygen-driven
ATRP
utilizing
alkylborane
compounds,
a
method
that
not
only
circumvents
need
for
stringent
removal
but
also
exploits
as
essential
cofactor
promote
This
approach
exhibits
broad
compatibility
in
organic
or
aqueous
media,
yielding
well-defined
polymers
with
low
dispersity
(Đ
1.11)
molecular
weights
closely
aligned
theoretical
values.
Triethylborane
(Et3B)
air-stable
triethylborane-amine
complex
(Et3B-DMAP)
facilitate
controlled
under
open-to-air
conditions,
demonstrating
efficiency
across
wide
range
of
monomers.
Moreover,
technique
enables
successful
synthesis
protein–polymer
conjugates
supports
surface
modifications
nanoparticles
silicon
wafers
aerobic
conditions.
represents
robust
versatile
platform
precision
far-reaching
implications
materials
science,
biomedicine,
advanced
engineering.
Polymer Chemistry,
Journal Year:
2022,
Volume and Issue:
14(3), P. 253 - 258
Published: Dec. 20, 2022
Retrieving
the
starting
monomers
from
polymers
synthesized
by
reversible
deactivation
radical
polymerization
has
recently
emerged
as
an
efficient
way
to
increase
recyclability
of
such
materials
and
potentially
enable
their
industrial
implementation.
To
date,
most
methods
have
primarily
focused
on
utilizing
high
temperatures
(typically
120
°C
180
°C)
trigger
depolymerization
reaction.
In
this
work,
we
show
that,
in
presence
Eosin
Y
under
light
irradiation,
a
much
faster
made
addition-fragmentation
chain-transfer
(RAFT)
can
be
triggered
even
at
lower
temperature
(