Abstract
The
development
of
advanced
materials
based
on
well‐defined
polymeric
architectures
is
proving
to
be
a
highly
prosperous
research
direction
across
both
industry
and
academia.
Controlled
radical
polymerization
techniques
are
receiving
unprecedented
attention,
with
reversible‐deactivation
chain
growth
procedures
now
routinely
leveraged
prepare
exquisitely
precise
polymer
products.
Reversible
addition‐fragmentation
transfer
(RAFT)
powerful
protocol
within
this
domain,
where
the
unique
chemistry
thiocarbonylthio
(TCT)
compounds
can
harnessed
control
vinyl
polymers.
With
intense
recent
focus
RAFT,
new
strategies
for
initiation
external
have
emerged
that
paving
way
preparing
polymers
demanding
applications.
In
work,
cutting‐edge
innovations
in
RAFT
opening
up
technique
broader
suite
researchers
explored.
Emerging
activating
TCTs
surveyed,
which
providing
access
into
traditionally
challenging
environments
polymerization.
latest
advances
future
perspectives
applying
RAFT‐derived
also
shared,
goal
convey
rich
potential
an
ever‐expanding
range
high‐performance
Bioprinting
is
a
tool
increasingly
used
in
tissue
engineering
laboratories
around
the
world.
As
an
extension
to
classic
engineering,
it
enables
high
levels
of
control
over
spatial
deposition
cells,
materials,
and
other
factors.
It
field
with
huge
promise
for
production
implantable
tissues
even
organs,
but
availability
functional
bioinks
barrier
success.
Extrusion
bioprinting
most
commonly
technique,
where
high-viscosity
solutions
materials
cells
are
required
ensure
good
shape
fidelity
printed
construct.
This
contradictory
hydrogels
which
generally
low
viscosity
prior
cross-linking
cell
viability,
making
them
not
directly
translatable
bioprinting.
review
provides
overview
important
rheological
parameters
methods
assess
printability,
as
well
effect
bioink
rheology
on
viability.
Developments
last
five
years
formulations
use
suspended
printing
overcome
limitations
then
discussed.
Chemical Reviews,
Год журнала:
2020,
Номер
120(5), С. 2950 - 3048
Опубликована: Фев. 21, 2020
The
past
decades
have
witnessed
an
increasing
interest
in
developing
advanced
polymerization
techniques
subjected
to
external
fields.
Various
physical
modulations,
such
as
temperature,
light,
electricity,
magnetic
field,
ultrasound,
and
microwave
irradiation,
are
noninvasive
means,
having
superb
but
distinct
abilities
regulate
polymerizations
terms
of
process
intensification
spatial
temporal
controls.
Gas
emerging
regulator
plays
a
distinctive
role
controlling
resembles
some
cases.
This
review
provides
systematic
overview
seven
types
external-field-regulated
polymerizations,
ranging
from
chain-growth
step-growth
polymerization.
A
detailed
account
the
relevant
mechanism
kinetics
is
provided
better
understand
each
field
In
addition,
given
crucial
modeling
simulation
mechanisms
investigation,
model
construction
typical
numerical
methods
used
this
well
highlights
interaction
between
experiment
toward
existing
systems
given.
At
end,
limitations
future
perspectives
for
critically
discussed.
state-of-the-art
research
progress
not
only
fundamental
principles
underlying
also
stimulates
new
development
methods.
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.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(10), С. 4678 - 4684
Опубликована: Фев. 25, 2022
The
ability
to
reverse
controlled
radical
polymerization
and
regenerate
the
monomer
would
be
highly
beneficial
for
both
fundamental
research
applications,
yet
this
has
remained
very
challenging
achieve.
Herein,
we
report
a
near-quantitative
(up
92%)
catalyst-free
depolymerization
of
various
linear,
bulky,
cross-linked,
functional
polymethacrylates
made
by
reversible
addition-fragmentation
chain-transfer
(RAFT)
polymerization.
Key
our
approach
is
exploit
high
end-group
fidelity
RAFT
polymers
generate
chain-end
radicals
at
120
°C.
These
trigger
rapid
unzipping
conventional
(e.g.,
poly(methyl
methacrylate))
bulky
poly(oligo(ethylene
glycol)
methyl
ether
polymers.
Importantly,
product
can
utilized
either
reconstruct
linear
polymer
or
create
an
entirely
new
insoluble
gel
that
also
subjected
depolymerization.
This
work
expands
potential
polymerization,
pushes
boundaries
depolymerization,
offers
intriguing
mechanistic
aspects,
enables
applications.
Chemical Society Reviews,
Год журнала:
2023,
Номер
52(9), С. 3035 - 3097
Опубликована: Янв. 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.
