Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 16, 2024
Abstract
Proton
transfer
is
essential
in
virtually
all
biochemical
processes,
with
enzymes
facilitating
this
by
optimizing
the
proximity
and
orientation
of
reactants
through
site‐specific
hydrogen
bonds.
also
crucial
rate‐determining
step
for
ring‐opening
polymerization
N
‐carboxyanhydrides
(NCAs),
widely
used
to
prepare
various
peptidomimetic
materials.
This
study
utilizes
side
chain‐assisted
strategy
accelerate
rate
chain
propagation
using
NCAs
tertiary
amine
pendants.
moiety
enables
bond
formation
between
incoming
NCA
polymer
amino
growing
end.
The
forms
a
proton
shuttle,
via
less
constrained
transition
state,
facilitate
process.
Moreover,
chains
enable
precipitation
monomers
situ
protonation
during
monomer
synthesis.
greatly
facilitates
synthesis
these
unreported
monomers,
allowing
direct
controlled
amine‐pendant
polypeptoids.
chain‐promoted
has
rarely
been
reported.
Additionally,
chains,
as
functional
groups,
endow
polymers
unique
properties
including
pH‐
thermo‐responsiveness,
tunable
p
K
s,
siRNA
transfection
capability.
self‐promoted
synthesis,
facile
preparation,
attractive
make
polypeptoids
promising
materials
applications.
Macromolecular Bioscience,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 22, 2025
Abstract
Cylindrical
bottlebrush
polymers
(CBPs)
enable
the
precise
adjustment
of
nanoparticle
properties
such
as
size,
shape,
and
functionality
exclusively
by
polymer
synthesis.
In
addition,
block
copolymer
side
chains
direct
access
to
core–shell
structure.
this
study,
synthesis
polypept(o)ides‐based
CBPs
is
presented
through
a
“grafting‐from”
strategy.
While,
poly‐lysine
(pLys)
serves
backbone,
poly(γ‐benzyl‐
l
‐glutamic
acid)‐block‐polysarcosine
(pGlu(OBn)‐
b
‐pSar)
copolymers
form
chains.
This
approach
enables
nanoparticles,
referred
brushes
(CSBs),
with
hydrodynamic
radius
(
R
h
)
from
17
70
nm,
molecular
weights
(1320–4000
kg
mol
−1
dispersity
indices
≈1.3
determined
size‐exclusion
chromatography.
Dasatinib
chosen
drug
molecule
model
explore
potential
synthetical
CSBs
platform
for
encapsulation
π
–
‐interactions.
An
overall
loading
efficiency
10%
achieved,
which
also
displayed
sustained
release
within
72
h,
cellular
uptake
into
human
glioblastoma
(U‐87
MG)
cells,
drug‐related
therapeutic
efficacy.
While
can
be
further
optimized
covalent
attachment,
these
results
establish
strong
foundation
use
in
nanomedicine.
Chemical Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
An
iterative
exponential
growth
(IEG)
strategy
relying
on
orthogonally
protected
monomers
is
developed
for
the
synthesis
of
peptoids.
This
a
scalable
technique
that
allows
precise
control
over
sequence,
chain
length,
and
stereoconfiguration.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(45)
Опубликована: Июль 29, 2024
Polythioesters
(PTEs)
are
emerging
sustainable
polymers
for
their
degradability
and
recyclability.
However,
low
polymerizability
of
monomers
extensive
side
reactions
often
hampered
the
polymerization
process.
Moreover,
copolymers
containing
both
thioester
other
types
functional
groups
in
backbone
highly
desirable
but
rarely
accomplished
owing
to
several
synthetic
challenges.
Here,
we
report
ring-opening
cascade
(ROCAP)
N-(2-(acetylthio)ethyl)-glycine
N-carboxyanhydrides
(TE-NCA)
afford
recyclable
PTEs
unprecedented
poly(thioester-co-peptoid)s
(P(TE-co-PP)s)
a
controlled
manner.
By
developing
appropriated
carboxylic
acid-tertiary
amine
dual
catalysts,
intramolecular
S-to-N
acyl
shift
is
coupled
into
ROCAP
process
TE-NCA
yield
products
with
dispersity
below
1.10,
molecular
weight
(M
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(46), С. 31849 - 31859
Опубликована: Ноя. 6, 2024
Spider
silk,
known
for
its
exceptional
tensile
strength,
extensibility,
and
toughness,
continues
to
inspire
advancements
in
polymer
materials
science.
Despite
extensive
research,
synthesizing
that
encompass
all
these
properties
remains
a
significant
challenge.
This
study
addresses
this
challenge
by
developing
high
molecular-weight
multiblock
synthetic
copolypeptides
mimic
the
hierarchical
structure
mechanical
of
spider
silk.
Using
autoaccelerated
ring-opening
polymerization
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 16, 2024
Abstract
Proton
transfer
is
essential
in
virtually
all
biochemical
processes,
with
enzymes
facilitating
this
by
optimizing
the
proximity
and
orientation
of
reactants
through
site‐specific
hydrogen
bonds.
also
crucial
rate‐determining
step
for
ring‐opening
polymerization
N
‐carboxyanhydrides
(NCAs),
widely
used
to
prepare
various
peptidomimetic
materials.
This
study
utilizes
side
chain‐assisted
strategy
accelerate
rate
chain
propagation
using
NCAs
tertiary
amine
pendants.
moiety
enables
bond
formation
between
incoming
NCA
polymer
amino
growing
end.
The
forms
a
proton
shuttle,
via
less
constrained
transition
state,
facilitate
process.
Moreover,
chains
enable
precipitation
monomers
situ
protonation
during
monomer
synthesis.
greatly
facilitates
synthesis
these
unreported
monomers,
allowing
direct
controlled
amine‐pendant
polypeptoids.
chain‐promoted
has
rarely
been
reported.
Additionally,
chains,
as
functional
groups,
endow
polymers
unique
properties
including
pH‐
thermo‐responsiveness,
tunable
p
K
s,
siRNA
transfection
capability.
self‐promoted
synthesis,
facile
preparation,
attractive
make
polypeptoids
promising
materials
applications.
ACS Central Science,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 29, 2024
Ring-opening
polymerization
on
N-carboxyanhydrides
(NCA)
initiated
by
primary
amines
has
been
the
dominantly
used
method
to
prepare
polypeptides
with
widespread
applications.
However,
this
chemistry
suffers
from
slow
rate,
limited
controllability,
and
difficulty
in
preparing
high
molecular
weight
polypeptides.
Herein,
we
develop
a
conjugated
cationic
catalyst
featuring
cation-dipole
interaction,
which
remarkably
enhances
reaction
rate
controllability
of
NCA
polymerization,
simultaneously,
afford
short
time
predictable
weights
(DP
=
20-500)
narrow
dispersities.
Experimental
data
computational
study
altogether
indicate
that
catalysts
manifest
single
center
triple
functions
activating
C5-carbonyl
NCAs
enhance
electrophilic
activity
monomer,
carbamate
intermediates
accelerate
decarboxylation,
moderately
passivating
improve
controllability.
Notably,
cationic-catalyst
is
well
recyclable
while
keeping
excellent
catalytic
performance.
Thus,
highly
efficient
strategy
implies
practical
promising
applications,
representing
new
avenue
design
for
chemistry.
Polymer Chemistry,
Год журнала:
2024,
Номер
15(13), С. 1318 - 1330
Опубликована: Янв. 1, 2024
In
situ
FTIR
monitoring
revealed
that
sarcosine
N
-carboxyanhydride
polymerisations
were
catalysed
using
a
lysine
dendrimer
macroinitiator
owing
to
hydrogen
bonding
interactions
between
the
core
and
monomer.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(45)
Опубликована: Июль 29, 2024
Abstract
Polythioesters
(PTEs)
are
emerging
sustainable
polymers
for
their
degradability
and
recyclability.
However,
low
polymerizability
of
monomers
extensive
side
reactions
often
hampered
the
polymerization
process.
Moreover,
copolymers
containing
both
thioester
other
types
functional
groups
in
backbone
highly
desirable
but
rarely
accomplished
owing
to
several
synthetic
challenges.
Here,
we
report
ring‐opening
cascade
(ROCAP)
N
‐(2‐(acetylthio)ethyl)‐glycine
‐carboxyanhydrides
(TE‐NCA)
afford
recyclable
PTEs
unprecedented
poly(thioester‐co‐peptoid)s
(P(TE‐co‐PP)s)
a
controlled
manner.
By
developing
appropriated
carboxylic
acid‐tertiary
amine
dual
catalysts,
intramolecular
S
‐to‐
acyl
shift
is
coupled
into
ROCAP
process
TE‐NCA
yield
products
with
dispersity
below
1.10,
molecular
weight
(
M
n
)
up
84.5
kDa,
precisely
ratio
peptoids.
Random
copolymerization
sarcosine
NCA
(Sar‐NCA)
gives
thioester‐embedded
polysarcosine
facile
degradation
while
maintaining
water
solubility.
This
work
represents
paradigm
ROP
NCAs,
enriches
realm
polymerizations,
provides
powerful
approach
P(TE‐co‐PP)s
that
otherwise
difficult
or
impossible
make.
