bioRxiv (Cold Spring Harbor Laboratory),
Год журнала:
2024,
Номер
unknown
Опубликована: Фев. 16, 2024
Pulmonary
drug
delivery
is
critical
to
the
treatment
of
respiratory
diseases.
However,
human
airway
surface
presents
multiscale
barriers
efficient
delivery.
Here
we
report
a
bottlebrush
polyethylene
glycol
(PEG-BB)
nanocarrier
that
can
translocate
across
all
within
surface.
Guided
by
molecular
theory,
design
PEG-BB
molecule
consisting
linear
backbone
densely
grafted
many
(∼1,000)
low
weight
(∼1000
g/mol)
PEG
chains;
this
results
in
highly
anisotropic,
wormlike
featuring
contour
length
∼250
nm,
cross-section
∼20
and
hydrodynamic
diameter
∼40
nm.
Using
classic
air-liquid-interface
culture
system
recapitulate
essential
biological
features
surface,
show
rapidly
penetrates
through
endogenous
mucus
periciliary
brush
layer
(mesh
size
20-40
nm)
be
internalized
cells
whole
epithelium.
By
quantifying
cellular
uptake
polymeric
carriers
various
architectures
manipulating
cell
proliferation
endocytosis
pathways,
translocation
epithelium
driven
architecture
enhanced
endocytosis.
Our
demonstrate
large,
polymers,
if
properly
designed,
used
as
novel
carrier
for
pulmonary
mucosal
Advanced Functional Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Авг. 30, 2024
Abstract
Hydrogels
are
explored
for
applications
in
agriculture,
water
purification,
and
biomedicine,
leveraging
softness,
elasticity,
high
uptake.
However,
hydrogels
notoriously
brittle,
especially
at
content.
This
shortcoming
puts
the
improvement
of
hydrogel
mechanics
forefront
current
research.
Yet
modern
strategies
enhancing
gel
resilience
come
expense
softness
swelling.
problem
is
addressed
using
bottlebrush
networks
with
disentangled
strands
hidden
length
reservoirs,
which
synergistically
enhance
swelling
robustness
while
maintaining
their
softness.
Implementing
a
facile
one‐pot
synthesis
single‐stranded
relatively
hydrophobic
poly(2‐hydroxyethyl
methacrylate)
(PHEMA)
backbone
hydrophilic
poly(2‐methyl‐2‐oxazoline)
(PMOx)
side
chains,
prepared
modulus
below
<1
kPa
ratios
up
to
125
that
can
withstand
10‐fold
extension.
A
bottlebrush
polymer
consists
of
a
long
linear
backbone
densely
grafted
with
many
relatively
short
side
chains.
widely
accepted
view
is
that
strong
steric
repulsion
among
the
highly
overlapped
chains
prestrains
backbone,
resulting
in
low
extensibility.
However,
we
recently
discovered
melt
polymers
incompatible
and
collapses
to
reduce
interfacial
free
energy,
regardless
Despite
this
discovery,
molecular
structure
these
so-called
"foldable"
their
assemblies
remains
poorly
understood.
Here,
present
deterministic
relationships
architecture,
mesoscopic
conformation,
macroscopic
properties
foldable
polymers.
combination
scaling
theory
experiments
reveals
as
chain
grafting
density
decreases,
diameter
increases,
whereas
end-to-end
distance
decreases.
These
behaviors
contradict
existing
understanding
polymers,
which
assumes
are
compatible.
Since
store
lengths
can
be
released
upon
large
deformations,
they
offer
way
decouple
intrinsic
stiffness-extensibility
trade-off
single-network
elastomers.
findings
provide
foundational
insights
into
using
building
blocks
for
designing
soft
(bio)materials.
Macromolecular Rapid Communications,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 4, 2025
Abstract
Bottlebrush
polymers
(BBPs)
have
emerged
as
a
special
class
of
macromolecules
composed
linear
backbone
the
main
chain
with
densely
grafted
polymeric
side
chains.
BBPs
present
many
unique
properties,
such
low
entanglement,
high
extension
backbone,
and
extremely
plateau
shear
moduli
relative
to
their
analogs
due
distinct
conformational
topological
characteristics.
This
review
summarizes
recent
significant
advances
BBPs,
from
synthetic
methods
versatile
properties
applications
in
areas
super‐soft
elastomers,
photonic
crystals,
self‐assembly,
friction,
biomimetic
tissues,
bio‐interfacial
interactions
enhance
cell
penetration
anti‐fouling
performance,
drug
delivery,
other
emerging
(polymer
electrolyte,
catalyst
support,
covalent
adaptable
networks).
Meanwhile,
molecular
dynamic
simulations
are
discussed
tool
disclose
relationship
between
structures
properties.
will
comprehensively
summarize
studies
on
point
out
direction
give
prediction
application
trend,
comment
future
BBPs.
Materials Advances,
Год журнала:
2023,
Номер
4(22), С. 5535 - 5545
Опубликована: Янв. 1, 2023
Designed
super-soft
and
solvent-free
bottlebrush
thermoplastic
elastomer
compatible
with
3D
printing
tunability
of
each
topological
parameter
at
the
molecular
level.
The
unique
architecture
of
bottlebrush
polymers
gives
rise
to
multiple
molecular
parameters
consisting
the
backbone
length
(Nbb),
side
chain
(Nsc),
and
grafting
density
(f).
These
macromolecules
can
thus
be
engineered
exhibit
a
wide
range
desired
properties,
enabling
their
use
in
applications
ranging
from
soft
elastomers
self-assembled
photonic
crystals.
However,
understanding
physical
behavior
throughout
this
design
space
is
challenging
due
significant
computational
cost
models.
In
work,
we
designed
coarse-grained
model
based
on
recently
developed
implicit
side-chain
(ISC)
framework
describe
conformation
melts.
Using
single
mean-field
(SCMF)
simulations,
used
observables
such
as
end–end
distance
⟨Rbb2⟩
radius
gyration
⟨Rg2⟩
parametrize
an
ISC
with
wormlike
cylinder
parameters;
effective
Kuhn
λ–1,
L
width
D.
We
considered
architectures,
systematically
varying
lengths
(Nbb
Nsc,
respectively)
f.
observed
that
conformations
follow
Gaussian
at
sufficiently
long
Nbb
are
much
more
flexible
than
analogous
chains
solution.
modest
stretching,
which
becomes
pronounced
high
densities
(f
=
5)
accommodate
crowded
chains.
Each
Nbb,
f
could
mapped
set
parameters,
so
they
represented
by
NISC
beads
size
D
bending
parameter
kθ
related
λ–1.
pairwise
interaction
potential
for
was
determined
using
iterative
Boltzmann
inversion
(IBI)
procedure
match
structural
features
ESC
model.
resulting
IBI
consistent
original
showing
similar
forms
relative
several
trends,
emergence
stronger
repulsive
longer
higher
densities,
attribute
increased
exclusion
neighboring
bottlebrushes
concentration
grafted
final
results
reduction
degrees
freedom
needed
melt
state,
expect
our
will
enable
efficient
large-scale
simulation
relate
macroscopic
properties
structure.
Macromolecules,
Год журнала:
2024,
Номер
57(21), С. 10379 - 10388
Опубликована: Окт. 21, 2024
The
conjugated
polymer's
backbone
conformation
dictates
the
delocalization
of
electrons,
ultimately
affecting
its
optoelectronic
properties.
Most
polymers
can
be
viewed
as
semirigid
rods
with
their
embedded
among
long
alkyl
side
chains.
Thus,
it
is
challenging
to
experimentally
quantify
a
backbone.
Here,
we
performed
contrast
variation
neutron
scattering
on
rigid
donor–acceptor
(D–A)
diketopyrrolopyrrole
(DPP)
selectively
deuterated
chains
measure
conformation.
We
first
synthesized
DPP-based
chains,
confirmed
by
NMR
and
FTIR.
Using
scattering,
found
that
are
much
more
than
poly(3-alkylthiophenes),
persistence
length
(Lp)
at
16–18
nm
versus
2–3
nm.
More
importantly,
in
relatively
flexible
poly(3-alkylthiophenes)
whose
whole
polymer,
has
same
Lp
value
compared
polymer
chain.
This
indicates
chain
interference
not
present
for
which
further
coarse-grained
molecular
dynamics
(CG-MD)
simulations.
Our
work
provides
novel
protocol
probe
paradigm-shifting
understanding
polymers.
Soft Matter,
Год журнала:
2023,
Номер
19(43), С. 8440 - 8452
Опубликована: Янв. 1, 2023
We
revisit
the
classic
scaling
model
of
a
cylindrical
polyelectrolyte
(PE)
brush
focusing
on
molecular
brushes
with
stiff
backbones
and
dispersions
polymer-decorated
nanorods.
Based
blob
representation
we
demonstrate
that
similarly
to
case
planar
PE
brushes,
separation
intra-
intermolecular
repulsions
between
charges
leads
novel
regimes
for
in
salt-added
solution
sharper
decrease
its
thickness
versus
salt
concentration
dependence.
These
theoretical
predictions
may
inspire
further
comprehensive
experimental
research
computer
simulations
synthetic
biopolyelectrolyte
brushes.
bioRxiv (Cold Spring Harbor Laboratory),
Год журнала:
2024,
Номер
unknown
Опубликована: Фев. 16, 2024
Pulmonary
drug
delivery
is
critical
to
the
treatment
of
respiratory
diseases.
However,
human
airway
surface
presents
multiscale
barriers
efficient
delivery.
Here
we
report
a
bottlebrush
polyethylene
glycol
(PEG-BB)
nanocarrier
that
can
translocate
across
all
within
surface.
Guided
by
molecular
theory,
design
PEG-BB
molecule
consisting
linear
backbone
densely
grafted
many
(∼1,000)
low
weight
(∼1000
g/mol)
PEG
chains;
this
results
in
highly
anisotropic,
wormlike
featuring
contour
length
∼250
nm,
cross-section
∼20
and
hydrodynamic
diameter
∼40
nm.
Using
classic
air-liquid-interface
culture
system
recapitulate
essential
biological
features
surface,
show
rapidly
penetrates
through
endogenous
mucus
periciliary
brush
layer
(mesh
size
20-40
nm)
be
internalized
cells
whole
epithelium.
By
quantifying
cellular
uptake
polymeric
carriers
various
architectures
manipulating
cell
proliferation
endocytosis
pathways,
translocation
epithelium
driven
architecture
enhanced
endocytosis.
Our
demonstrate
large,
polymers,
if
properly
designed,
used
as
novel
carrier
for
pulmonary
mucosal
