Macromolecules,
Год журнала:
2023,
Номер
56(13), С. 5101 - 5110
Опубликована: Июнь 26, 2023
Zinc
oxide
(ZnO)
was
previously
reported
as
an
excellent
cocatalyst
for
mechanically
controlled
atom
transfer
radical
polymerization
(mechanoATRP),
but
its
photocatalytic
properties
in
photoinduced
ATRP
(photoATRP)
have
been
much
less
explored.
Herein,
well-defined
ZnO
nanocrystals
were
prepared
via
microwave-assisted
synthesis
and
applied
a
heterogeneous
mechano-
photoATRP.
Both
techniques
yielded
polymers
with
outstanding
control
over
the
molecular
weight,
ZnO-cocatalyzed
photoATRP
faster
than
analogous
mechanoATRP
(conversion
of
91%
1
h
vs
54%
5
h).
The
kinetics
tuned
by
loadings
nanocrystals.
PhotoATRP
did
not
require
any
excess
ligand
versus
Cu,
contrast
to
mechanoATRP,
requiring
ligand,
acting
reducing
agent.
proceeded
controllably
without
prior
deoxygenation,
since
involved
cascade
reactions,
leading
rapid
elimination
oxygen.
versatility
robustness
technique
demonstrated
various
(meth)acrylate
monomers
good
temporal
preservation
end-group
functionality,
illustrated
formation
tailored
block
copolymers.
Chemical Reviews,
Год журнала:
2021,
Номер
122(2), С. 2292 - 2352
Опубликована: Дек. 9, 2021
The
halogen-atom
transfer
(XAT)
is
one
of
the
most
important
and
applied
processes
for
generation
carbon
radicals
in
synthetic
chemistry.
In
this
review,
we
summarize
highlight
aspects
associated
with
XAT
impact
it
has
had
on
photochemistry
photocatalysis.
organization
material
starts
analysis
mechanistic
then
follows
a
subdivision
based
nature
reagents
used
halogen
abstraction.
This
review
aims
to
provide
general
overview
fundamental
concepts
main
agents
involved
objective
offering
tool
understand
facilitate
development
new
radical
strategies.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(34), С. 15413 - 15430
Опубликована: Июль 26, 2022
Since
its
inception,
atom
transfer
radical
polymerization
(ATRP)
has
seen
continuous
evolution
in
terms
of
the
design
catalyst
and
reaction
conditions;
today,
it
is
one
most
useful
techniques
to
prepare
well-defined
polymers
as
well
notable
examples
catalysis
polymer
chemistry.
This
Perspective
highlights
fundamental
advances
ATRP
reactions
catalysts,
focusing
on
crucial
role
that
mechanistic
studies
play
understanding,
rationalizing,
predicting
outcomes.
A
critical
summary
traditional
systems
provided
first;
we
then
focus
recent
developments
improve
selectivity,
control
polymerizations
via
external
stimuli,
employ
new
photochemical
or
dual
catalytic
with
an
outlook
future
research
directions
open
challenges.
Reversible-deactivation
radical
polymerizations
(RDRPs)
have
revolutionized
synthetic
polymer
chemistry.
Nowadays,
RDRPs
facilitate
design
and
preparation
of
materials
with
controlled
architecture,
composition,
functionality.
Atom
transfer
polymerization
(ATRP)
has
evolved
beyond
traditional
field,
enabling
synthesis
organic-inorganic
hybrids,
bioconjugates,
advanced
polymers
for
electronics,
energy,
environmentally
relevant
polymeric
broad
applications
in
various
fields.
This
review
focuses
on
the
relation
between
ATRP
technology
12
principles
green
chemistry,
which
are
paramount
guidelines
sustainable
research
implementation.
The
features
presented,
discussing
environmental
and/or
health
issues
challenges
that
remain
to
be
overcome.
Key
discoveries
recent
developments
highlighted,
while
providing
a
perspective
future
opportunities
this
area.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(23)
Опубликована: Фев. 7, 2022
The
application
of
photochemistry
in
polymer
synthesis
is
interest
due
to
the
unique
possibilities
offered
compared
thermochemistry,
including
topological
and
temporal
control,
rapid
polymerization,
sustainable
low-energy
processes,
environmentally
benign
features
leading
established
emerging
applications
adhesives,
coatings,
adaptive
manufacturing,
etc.
In
particular,
utilization
controlled/living
polymerizations
often
offers
capability
for
precise
control
over
macromolecular
structure
chain
length
addition
associated
advantages
photochemistry.
Herein,
latest
developments
photocontrolled
living
radical
cationic
their
combinations
syntheses
are
discussed.
This
Review
summarizes
highlights
recent
studies
area
photoinduced
polymerizations.
A
discussion
mechanistic
details
differences
as
well
parallels
between
different
systems
polymerization
methods
monomer
applicability.
Chemical Science,
Год журнала:
2022,
Номер
13(39), С. 11540 - 11550
Опубликована: Янв. 1, 2022
Photoinduced
atom
transfer
radical
polymerization
(photo-ATRP)
has
risen
to
the
forefront
of
modern
polymer
chemistry
as
a
powerful
tool
giving
access
well-defined
materials
with
complex
architecture.
However,
most
photo-ATRP
systems
can
only
generate
radicals
under
biocidal
UV
light
and
are
oxygen-sensitive,
hindering
their
practical
use
in
synthesis
biohybrids.
Herein,
inspired
by
photoinduced
electron
transfer-reversible
addition-fragmentation
chain
(PET-RAFT)
polymerization,
we
demonstrate
dual
photoredox/copper
catalysis
that
allows
open-air
ATRP
green
irradiation.
Eosin
Y
was
used
an
organic
photoredox
catalyst
(PC)
combination
copper
(X-Cu
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(44), С. 24315 - 24327
Опубликована: Окт. 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.
European Polymer Journal,
Год журнала:
2024,
Номер
211, С. 113001 - 113001
Опубликована: Март 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.
Chemical Communications,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 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.
