Far-From-Equilibrium Processing Opens Kinetic Paths for Engineering Novel Materials by Breaking Thermodynamic Limits
ACS Materials Letters,
Год журнала:
2024,
Номер
7(1), С. 319 - 332
Опубликована: Дек. 20, 2024
Thermodynamic
metastable
nanomaterials
display
attractive
properties
due
to
their
unique
atom
configuration
and
microstructure,
distinct
from
counterparts
found
in
equilibrium
phase
diagrams.
However,
fabrication
remains
a
grand
challenge
because
conventional
methods
are
generally
operated
under
near-equilibrium
conditions.
To
break
the
thermodynamic
limits
for
discovering
novel
materials,
numerous
by
adopting
extreme
strategies
have
been
developed,
including
ultrafast
synthesis,
Joule
heating,
carbon
thermal
shock,
pulse
temperature
gradients,
rapid
solidification.
A
common
feature
of
these
is
that
target
material
processed
far-from-equilibrium
(FFE)
state,
where
new
kinetic
route
created
evolution
an
unprecedented
composition/structure.
In
this
review,
we
provide
unifying
view
guiding
engineering
FFE
environments
during
materials
categorized
within
both
temporal
spatial
dimensions
landscape.
Furthermore,
highlight
potential
not
only
as
platforms
deeper
understanding
nonequilibrium
behaviors,
but
also
framework
designing
innovative
advanced
technologies.
Язык: Английский
Water Transport Dynamics and Kinetic Equilibria in Nanoblisters at the Graphene–Mica Interface
Joshua S. Roys,
Nicholas D. Stucchi,
Jennifer M. O’Brien
и другие.
Langmuir,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 4, 2025
Nanoscale
reduced
volumes
with
novel
properties
can
be
produced
from
2D
materials
like
graphene.
Mild
thermal
annealing
imposes
vast
and
varied
amounts
of
water
intercalation
into
the
graphene–mica
interface,
resulting
in
formation
nanoblisters
impacting
local
environment
for
applications
such
as
reactions
confined
at
solid–solid
interface.
Atomic
force
microscopy
imaging
(AFM)
micro-Fourier
transform
infrared
(micro-FTIR)
spectroscopy
characterization
after
60–120
°C
anneals
revealed
large
readily
intercalate
nanoblisters,
elucidating
transport
behavior
under
mild
reaction
conditions.
The
inflation
deflation
graphene
throughout
process
is
attributed
to
contraction
capping
layer
upon
cooling
temperature,
due
independence
nanoblister
aspect
ratios
volume
or
surface
area.
intercalated
was
estimated
by
distended
each
exhibit
an
equilibrium
trend
established
2
h
annealing.
This
occurs
a
variety
temperatures,
but
higher
temperatures
favor
distention
accommodate
larger
water.
Nanoblister
are
set
during
process,
indicating
kinetic
trapping
effect
that
influence
physical
reactivity
all
systems
Язык: Английский
Chemical degradation as an enabling pathway to polymersome functionalization
RSC Advances,
Год журнала:
2025,
Номер
15(6), С. 4693 - 4700
Опубликована: Янв. 1, 2025
Factors
like
nature
of
the
m-RAFT,
oxygen,
and
temperature
are
crucial
in
chemical
degradation,
which
functionalizes
polymersomes,
allowing
them
to
manifest
Phoenix
dynamics,
whereby
they
exhibit
growth-implosion
cycles
population
growth.
Язык: Английский
Self-assembled Nanostructures of Noncovalent Giant Amphiphilic Molecules Composed of Hydrophobic Isobutyl BPOSS and Hydrophilic POM in Different Cosolvents
Langmuir,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 21, 2025
The
self-assembly
of
giant
amphiphilic
molecules
with
diverse
topological
structures
has
been
widely
investigated
in
bulk,
solution,
and
interfacial
environments
because
it
can
lead
to
interesting
geometric
patterns.
However,
many
or
their
self-assembling
units
are
built
by
covalent
bonds,
which
may
limit
the
movement
molecular
blocks,
affecting
process
microstructure.
In
contrast,
noncovalent
interactions
nanomorphologies
nanostructures.
this
study,
we
(BPOSS&POM)
forming
electrostatic
between
hydrophobic
isobutyl
polyhedral
oligomeric
silsesquioxanes
(BPOSSs)
hydrophilic
polyoxometalates
(POMs)
investigate
behavior
water/acetone,
water/THF,
hexane/acetone
cosolvents.
By
controlling
solvent
parameters,
BPOSS&POM
self-assembled
into
nanosheet,
nanobelt,
nanosphere,
nanocrumb
structures.
morphology
detailed
nanostructure
different
self-assemblies
were
revealed
performing
transmission
electron
microscopy
(TEM),
scanning
(SEM),
small-angle
X-ray
scattering
(SAXS)
measurements.
TEM
SAXS
results
indicated
that
microphase
exhibited
a
lamellar
structure
an
interlayer
distance
about
3
nm.
was
alternatively
organized
layers
BPOSS
POM
according
size
dimension.
polarity
solvents
substantially
affected
nanoassemblies
but
not
aggregation
POM.
This
research
offers
insights
preparation
nanomaterials
micromorphologies
simply
adjusting
solution
components.
Язык: Английский
Observation of Dynamic Aggregation Behavior in Thermoresponsive Micro- and Nanoparticles via Diffusion-Ordered NMR Spectroscopy
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 7, 2025
Stimuli-responsive
drug
delivery
systems
have
expanded
the
diversity
of
potential
cargos
by
protecting
payloads,
extending
circulation,
and
controlling
payload
release.
However,
quantitative
characterization
methods
that
accurately
describe
these
complex
are
needed
to
accelerate
their
translation
clinic.
To
this
extent,
degradable,
thermoresponsive
polyesters
were
developed
through
ring-opening
copolymerization
maleic
anhydride
an
oligo(ethylene
glycol)-functionalized
epoxide.
The
resulting
polymers
possess
a
lower
critical
solution
temperature
such
they
soluble
in
aqueous
solutions
at
low
temperatures
(4-7
°C)
but
assemble
into
particles
above
room
(25
°C).
particle
size
morphology
tunable
selection
polymer
initiator,
forming
nanoparticle
(ca.
162
nm)
microparticle
1.85
μm)
assemblies
using
macromolecular
polyethylene
glycol
small
molecule
propargyl
alcohol
initiators,
respectively.
Diffusion-ordered
NMR
spectroscopy
(DOSY)
was
used
over
range
develop
molecular
weight
calibrations
certified
poly(ethylene
glycol)
standards.
DOSY
able
monitor
dynamic
self-assembly
behavior
solutions,
distinct
diffusion
constant
shifts,
quantify
aggregation
number
intermediates
within
nano-
microparticles.
Язык: Английский
Quantized Fusion Kinetics in Block Copolymer Micelles
ACS Macro Letters,
Год журнала:
2025,
Номер
unknown, С. 391 - 395
Опубликована: Март 12, 2025
The
fusion
kinetics
of
block
copolymer
micelles
in
dilute
solutions
have
been
investigated.
As
a
model
system,
1,2-polybutadiene-block-poly(ethylene
oxide)
the
ionic
liquid
1-butyl-3-methylimidazolium
tetrafluoroborate
studied.
is
selective
solvent
for
poly(ethylene
oxide),
promoting
self-assembly
into
spherical
micelles.
Furthermore,
quality
corona
near-theta,
thereby
reducing
large
steric
barrier
to
fusion.
Small,
kinetically
trapped
were
prepared
using
cosolvent,
and
subsequently
monitored
via
dynamic
light
scattering
at
elevated
temperatures.
Small-angle
X-ray
cryo-transmission
electron
microscopy
quantified
significant
increases
mean
aggregation
number
after
thermal
annealing
confirmed
formation
well-defined,
larger
For
higher
temperatures,
process
occurs
two
steps,
with
relaxation
time
second
step
being
least
an
order
magnitude
longer
than
first.
Interestingly,
steady-state
first
had
approximately
twice
starting
number,
those
four
times
original
value.
This
result
strongly
suggests
quantization
effect,
where
rate
much
slower
micelles,
presumably
due
enhanced
crowding.
also
increasing
function
concentration,
consistent
dominant
mechanism.
Язык: Английский
Advancements in Targeted Therapies for Colorectal Cancer: Innovative Drug Formulation and Delivery Strategies
Archiv der Pharmazie,
Год журнала:
2025,
Номер
358(4)
Опубликована: Апрель 1, 2025
ABSTRACT
Colorectal
cancer
(CRC)
is
a
leading
cause
of
cancer‐related
mortality
globally,
with
increasing
incidence
presenting
significant
treatment
challenges.
Traditional
nontargeted
therapies
often
result
in
high
toxicity
and
limited
efficacy,
underscoring
the
need
for
improved
modalities.
This
review
highlights
recent
advancements
drug
delivery
systems
to
enhance
therapeutic
outcomes
CRC.
We
examine
innovative
strategies,
including
computer‐assisted
pharmaceutical
formulation,
sustained‐release
matrices,
prodrugs,
as
well
targeted
mechanisms
such
exosomes,
liposomes,
hydrogels,
antibody‐drug
conjugates,
stimuli‐responsive
systems.
These
methodologies
offer
biodistribution,
enhanced
targeting
cells,
reduced
off‐target
effects,
promising
better
clinical
outcomes.
Additionally,
we
discuss
development
novel
formulations
designed
optimize
agents
advanced
Ongoing
trials
investigating
these
signify
shift
toward
more
effective
patient
options.
While
challenges
remain
application
therapies,
continued
research
offers
avenues
improving
study
aims
inform
future
strategies
managing
this
aggressive
disease,
ultimately
enhancing
survival
rates
quality
life
affected
individuals.
Язык: Английский
Supramolecular Systems Chemistry Based on the Interplay between Peptides and Porphyrins
ChemSystemsChem,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 23, 2024
Abstract
The
functions
of
living
organisms
are
emergent
from
networks
biomolecules.
In
this
review,
we
discuss
the
creation
synthetic
life‐like
systems
based
on
interplay
peptides
and
porphyrins
in
supramolecular
chemical
systems.
particular,
focus
spatiotemporal
control
self‐assembly
processes,
which
allows
for
development
hierarchical
structures
biomimetic
catalysis
adaptive
dynamics
stimulus‐responsive
structural
transformations.
Notably,
when
operating
a
nonequilibrium
regime–characterized
by
kinetic
traps,
feedback
loops,
dissipative
conditions–the
landscape
expands
system‐level
properties
emerge,
including
transient
catalysis,
metabolic
self‐replication,
Darwinian‐like
evolution.
Controlling
these
at
biointerface
would
facilitate
intelligent
therapeutic
interventions
anti‐tumor
phototherapy.
Supramolecular
chemistry
provides
valuable
framework
exploring
new
physicochemical
spaces
porphyrins,
may
offer
distinct
advantages
extensive
applications
across
diverse
fields.
Язык: Английский