Macromolecules,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 3, 2024
High-refractive-index
polymers
are
important
materials
in
optoelectronics.
Cyclic
olefin
copolymers
(COCs)
among
the
most
promising
optical
materials;
however,
high-refractive-index
COCs
still
remain
unsolved
but
highly
desired.
In
this
study,
principles
for
designing
all-hydrocarbon
were
proposed.
Diverse
prepared
by
zirconium-catalyzed
coordination–insertion
copolymerization
of
nine
types
aromatic
group-containing
cyclic
olefins
with
ethylene.
polymers,
these
have
significantly
higher
refractive
indices
>1.60,
>1.65,
and
>1.70
compared
to
previous
values
at
moderate
incorporation
(maximum:
35.7
mol%)
optically
transparent
(90%–94%)
visible
wavelength
range.
Furthermore,
amorphous,
a
wide
Tg
range
92–262
°C,
exhibit
high
thermal
stability
(Td,5%
=
372–442
°C),
possess
extremely
low
hygroscopicity
<0.01%.
These
merits
indicate
their
potential
as
materials.
Advanced Science,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 16, 2024
Abstract
Mechanically
robust
and
tough
polymeric
materials
are
in
high
demand
for
applications
ranging
from
flexible
electronics
to
aerospace.
However,
achieving
both
toughness
strength
polymers
remains
a
significant
challenge
due
their
inherently
contradictory
nature.
Here,
universal
strategy
enhancing
the
of
polymer
blends
using
ligand‐modulated
metal–organic
framework
(MOF)
nanoparticles
is
presented,
which
engineered
have
adjustable
hydrophilicity
lipophilicity
by
varying
types
ratios
ligands.
Molecular
dynamics
(MD)
simulations
demonstrate
that
these
can
effectively
regulate
interfaces
between
chemically
distinct
based
on
amphiphilicity.
Remarkably,
mere
0.1
wt.%
MOF
with
optimized
amphiphilicity
(ML‐MOF
(5:5)
)
delivered
≈1.1‐
≈34.1‐fold
increase
poly
(lactic
acid)
(PLA)/poly
(butylene
succinate)
(PBS)
blend,
respectively.
Moreover,
amphiphilicity‐tailorable
universally
enhance
mechanical
properties
various
blends,
such
as
polypropylene
(PP)/polyethylene
(PE),
PP/polystyrene
(PS),
PLA/poly
adipate‐co‐terephthalate)
(PBAT),
PLA/polycaprolactone
(PCL)/PBS.
This
simple
method
offers
potential
strengthening
toughening
blends.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(18), P. 3828 - 3833
Published: April 29, 2024
The
photocatalyzed
radical-triggered
thio/selenosulfonylation–bicyclization
of
indole-tethered
1,6-enynes
has
been
established
for
the
first
time,
enabling
synthesis
various
previously
unreported
thio/selenosulfonylated
benzo[c]pyrrolo[1,2,3-lm]carbazoles
with
moderate
to
good
yields
under
mild
conditions.
reaction
pathway
was
proposed,
consisting
energy
transfer,
homolytic
cleavage,
radical
addition,
5-exo-dig,
coupling,
and
a
Mallory
cascade.
This
approach
exhibits
wide
substrate
compatibility
excellent
tolerability
toward
functional
groups
is
characterized
by
its
remarkable
efficiency
in
both
bond
formation
annulation.
Green Chemistry,
Journal Year:
2025,
Volume and Issue:
27(7), P. 1974 - 1983
Published: Jan. 1, 2025
We
present
a
tetrabutylammonium
fluoride
(TBAF)-catalyzed
inverse
vulcanization
(IV)
process
that
extends
the
methodology
for
anionic
IV
polymerisation
under
mild
conditions
and
broadens
potential
application
areas
of
resulting
polymers.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: Feb. 25, 2025
The
precise
placement
of
thioester
bonds
into
sequence-controlled
polymers
remains
a
grand
challenge.
Here,
we
demonstrate
the
versatile
synthesis
from
step
polymerization
cyclic
thioanhydrides
(A),
diacrylates
(B),
and
diols/diamines
(C).
In
addition
to
easily
accessible
diverse
monomers,
method
is
metal-free/catalyst-free,
atom-economical,
wide
in
monomer
scope,
yielding
107
with
>90%
yields
weight-average
molecular
weights
up
175.4
kDa.
obtained
contain
ABAC-type
repeating
units
precisely
distributed
in-chain
ester
(and
amide)
groups.
chemoselectivity
revealed
by
density
functional
theory
calculations.
polymer
library
exhibits
considerably
tunable
performance:
glass-transition
temperatures
−36–72
°C,
melting
43–133
degradability,
thermoplastics/elastomers,
thioester-based
functions.
This
study
furnishes
facile
incorporate
polymers.
challenging.
authors
thioanhydrides,
diacrylates,
diols/diamines.
Macromolecular Rapid Communications,
Journal Year:
2024,
Volume and Issue:
45(17)
Published: June 2, 2024
As
the
demand
for
sustainable
polymers
increases,
most
research
efforts
have
focused
on
polyesters,
which
can
be
bioderived
and
biodegradable.
Yet
analogous
polythioesters,
where
one
of
oxygen
atoms
has
been
replaced
by
a
sulfur
atom,
remain
relatively
untapped
source
potential.
The
incorporation
allows
polymer
to
exhibit
wide
range
favorable
properties,
such
as
thermal
resistance,
degradability,
high
refractive
index.
Polythioester
synthesis
represents
frontier
in
research,
holding
promise
paving
way
eco-friendly
alternatives
conventional
polyesters.
Moreover,
polythioester
also
open
avenues
development
recyclable
materials.
In
last
25
years,
many
methods
synthesize
polythioesters
developed.
However,
date
no
industrial
developed
due
challenges
costs,
yields,
toxicity
by-products.
This
review
will
summarize
recent
advances
synthesis,
covering
step-growth
polymerization,
ring-opening
polymerization
(ROP),
biosynthesis.
Crucially,
benefits
processes
highlighted,
paying
particular
attention
their
sustainability,
with
aim
encouraging
further
exploration
into
fast-growing
field
polythioesters.
Polymer Reviews,
Journal Year:
2024,
Volume and Issue:
unknown, P. 1 - 65
Published: Nov. 20, 2024
The
biomedical
industry
has
witnessed
a
transformative
evolution
with
the
advent
of
3D
printing
technology.
However,
inherent
limitations,
such
as
inability
to
produce
dynamic
human
tissues
due
absence
temporal
dimension,
have
persisted,
resulting
in
static
and
inanimate
printed
products.
To
address
this
challenge
enable
creation
living
constructs,
concept
4D
emerged,
marking
paradigm
shift
additive
manufacturing.
In
printing,
time
becomes
fourth
breathing
life
into
previously
creations.
This
review
paper
explores
journey
from
pivotal
role
manufacturing
process.
Specifically,
it
highlights
integration
time-dependent
responsive
materials,
focusing
on
stimuli-responsive
hydrogels,
cornerstone
advancements.
These
materials
exhibit
remarkable
ability
adapt
respond
various
stimuli,
encompassing
physical,
chemical,
biological
signals.
delves
recent
publications
synergy
between
these
stimuli
shedding
light
their
intricate
interactions
potential
applications.
One
primary
areas
interest
lies
medical
applications,
notably
tissue
engineering,
where
holds
immense
promise.
utilization
creating
biomimetic
scaffolds
that
can
dynamically
complex
environments.
Furthermore,
discusses
technical
considerations
prospects
technology,
emphasizing
its
revolutionize
landscape.
amalgamation
opens
new
avenues
for
personalized
medicine,
localized
drug
delivery,
regenerative
therapies,
bridging
gap
requirements
modern
healthcare.
present
offers
complete
examination
evolution,
challenges,
paving
way
innovations
field.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(29)
Published: April 29, 2024
Abstract
Isotactic
polythioesters
(PTEs)
that
are
thioester
analogs
to
natural
polyhydroxyalkanoates
(PHAs)
have
attracted
growing
attention
due
their
distinct
properties.
However,
the
development
of
chemically
synthetic
methods
for
preparing
isotactic
PTEs
has
long
been
an
intricate
endeavour.
Herein,
we
report
successful
synthesis
perfectly
via
stereocontrolled
ring‐opening
polymerization.
This
binaphthalene‐salen
aluminium
(SalBinam‐Al)
catalyst
promoted
a
robust
polymerization
rac
‐α‐substituted‐β‐propiothiolactones
(
‐BTL
and
‐PTL)
with
highly
kinetic
resolution,
affording
P(BTL)
P(PTL)
M
n
up
276
kDa.
Impressively,
formed
supramolecular
stereocomplex
improved
thermal
property
T
m
=204
°C).
Ultimately,
this
resolution
enabled
facile
isolation
enantiopure
S
)‐BTL,
which
could
efficiently
convert
important
pharmaceutical
building
block
)‐2‐benzyl‐3‐mercapto‐propanoic
acid.
served
as
tough
ductile
material
comparable
commercialized
polyolefins.
system
allowed
access
PTEs,
establishing
powerful
platform
discovery
sustainable
plastics.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(26), P. 18074 - 18082
Published: June 21, 2024
A
cyclic
thioenone
system
capable
of
controlled
ring-opening
polymerization
(ROP)
is
presented
that
leverages
a
reversible
Michael
addition-elimination
(MAE)
mechanism.
The
monomers
are
easy
to
access
and
modify
for
the
first
time
incorporate
dynamic
reversibility
MAE
with
chain-growth
polymerization.
This
strategy
features
mild
conditions,
tunable
functionalities,
molecular
weights
(
Advanced Functional Materials,
Journal Year:
2024,
Volume and Issue:
34(44)
Published: May 20, 2024
Abstract
Advancements
in
the
synthesis
of
sulfur‐rich
materials
are
driving
progress
across
diverse
fields
owing
to
rich
and
tunable
functionalities
those
materials.
These
typically
valued
for
their
electrochemical
behaviors,
high
refractive
indices,
heavy
metal
affinity,
ability
form
dynamic
covalent
bonding.
As
a
result,
applications
span
various
industries
including
electronics,
catalysis,
lithium‐sulfur
batteries,
water
reclamation,
optoelectronics.
Moreover,
elemental
sulfur,
byproduct
petroleum
industry,
is
produced
abundantly,
necessitating
exploration
novel
valorization
routes
polymers
made
from
this
feedstock.
The
unique
combination
properties
also
makes
them
an
ideal
platform
development
high‐performance
functional
coatings,
offering
durability
tailored
protective
thus
enhancing
lifespan
performances
variety
environmental
conditions.
presence
bonds
many
enables
creation
self‐healing
while
sulfur
itself
or
comonomers
can
contribute
antimicrobial,
antifouling,
corrosion‐resistant
properties.
Furthermore,
have
potential
be
used
design
icephobic
superhydrophobic
coatings.
This
underscores
versatility
as
advanced
coatings
with
superior
