ACS Applied Materials & Interfaces,
Год журнала:
2024,
Номер
16(43), С. 58973 - 58979
Опубликована: Окт. 18, 2024
Maximizing
the
molecular
information
density
requires
simultaneously
functionalizing
distinct
monomers
and
their
coupling
connections.
However,
current
synthesis
generally
focuses
on
rather
than
reactions
because
multistep
significantly
escalate
synthetic
complexity
in
an
exponential
increase.
Here,
we
report
two-dimensional
nanoarchitectures
(2DNs)
of
end-on
oligomers,
with
versatile
structures
negative
differential
resistance
(NDR),
synthesized
by
programmed
surface-initiated
step
electrosynthesis
based
simultaneous
utilization
six
including
cross-
homocouplings.
The
resulting
vertically
similar
values
thickness
length,
as
crystalline
2DNs,
exhibit
subnanometer
uniformity,
ultrahigh
compressive
modulus
40
GPa,
low-bias
NDR
at
0.13
V
ultralow
power
consumption
down
to
0.05
nW/μm2.
This
highly
controlled
provides
a
unique
dimension
enhance
structural
diversity
2D
nanomaterials
for
high-density
low-power
electronics.
Biopolymer
sequences
dictate
their
functions,
and
protein-based
polymers
are
a
promising
platform
to
establish
sequence–function
relationships
for
novel
biopolymers.
To
efficiently
explore
vast
sequence
spaces
of
natural
proteins,
repetition
is
common
strategy
tune
amplify
specific
functions.
This
applied
repeats-in-toxin
(RTX)
proteins
with
calcium-responsive
folding
behavior,
which
stems
from
tandem
repeats
the
nonapeptide
GGXGXDXUX
in
X
can
be
any
amino
acid
U
hydrophobic
acid.
determine
functional
range
this
nonapeptide,
we
modified
naturally
occurring
RTX
protein
that
forms
β-roll
structures
presence
calcium.
Sequence
modifications
focused
on
calcium-binding
turns
within
repetitive
region,
including
either
global
substitution
nonconserved
residues
or
complete
replacement
consensus
GGAGXDTLY.
Some
disrupted
typical
transition
intrinsically
disordered
random
coils
folded
β
rolls,
despite
conservation
underlying
sequence.
Proteins
enriched
smaller,
acids
adopted
secondary
absence
calcium
underwent
structural
rearrangement
calcium-rich
environments.
In
contrast,
bulkier,
hydrophilic
maintained
intrinsic
disorder
These
results
indicate
significant
role
folding,
thereby
revealing
leverage
design
tunable,
Polymer Chemistry,
Год журнала:
2024,
Номер
15(47), С. 4864 - 4874
Опубликована: Янв. 1, 2024
Recombinant
protein
engineering
accelerated
the
synthesis
of
sequence-defined,
calcium-responsive
biopolymers.
A
mutation
panel
repeats-in-toxin
(RTX)
proteins
revealed
sequence-dependent
disorder,
calcium
sensitivity,
and
structural
transitions.
Macromolecules,
Год журнала:
2024,
Номер
57(21), С. 10454 - 10462
Опубликована: Окт. 23, 2024
Coil–globule
transition
in
a
single-chain
polymer
is
the
cornerstone
of
physics.
Although
completely
understood
for
homopolymers,
it
turns
out
to
be
much
more
sophisticated
copolymers
mere
two
nonionic
monomers
because
position
and
especially
sharpness
(cooperativity)
conformational
change
them
are
highly
sequence-dependent.
In
this
work,
statistical
theory
coil–globule
neutral
AB
with
regular
sequences
developed.
To
describe
role
primary
structure,
we
go
beyond
mean-field
approximation
calculate
Gaussian
fluctuation
correction
due
chemical
differences
(incompatibility)
between
A
B
monomers.
Local
compositional
fluctuations
reduce
second
third
virial
coefficients
monomer
interactions;
these
corrections
found
general
form,
closed-form
expressions
provided
block-alternating
chains
block
length
m.
For
nonperiodic
sequences,
annealed
averages.
Increasing
blockiness
shown
(i)
make
globule
denser,
(ii)
shift
higher
temperatures,
and,
most
importantly,
(iii)
narrow
region.
The
collapse
sharpens
strongly
when
accompanied
or
shortly
followed
by
intraglobular
microphase
separation.
developed
contributes
comprehensive
understanding
sequence-tunable
behavior
macromolecules,
including
Khokhlov–Khalatur
protein-like
forming
globules
core–shell
microstructure.
Six
different
flexible
stereocontrolled
oligo(triazole-urethane)s
substituted
by
precise
sequences
of
nucleobases
or
analogs
are
synthesized.
Molecular
dynamics
simulations
indicate
that
the
flexibility
backbone
leads
to
unspecific
complexation
pairs
oligomers,
irrespective
complementarity
their
sequences.
This
is
ascribed
existence
other
interactions
between
as
well
spatial
blurring
sequence
order
encoded
in
chemical
structure
chain
due
its
flexibility.
The
same
conclusions
drawn
when
investigating
irreversible
adsorption
probe
oligomers
onto
a
layer
target
grafted
click
chemistry
mushroom
configuration
on
silicon
substrate.
In
contrast,
denser
brush
configurations,
becomes
more
specific,
with
it
being
twice
probable
chains
complementary
would
be
irreversibly-bound
than
those
non-complementary
sequence.
lateral
excluded
volume
brush,
leading
partial
stretching
and
increased
preservation
information
contained
monomer
chains.
At
even
higher
grafting
densities,
however,
penetration
increasingly
difficult,
resulting
loss
binding
efficiency.
Our
work
thus
demonstrates
adverse
role
specificity
nucleobase-functionalized
provides
directions
for
an
improvement
tuning
density
Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 16, 2024
Abstract
The
selective
monoaddition
of
polymerizable
vinyl
monomers
like
styrenes
and
methacrylates
in
a
living
manner
has
been
achieved
for
the
flash‐flow
preparation
molecules
defined
sequence
with
high
selectivity.
We
demonstrated
sequence‐defined
synthesis
multifunctional
using
an
initiator,
functionalized
styrenes,
diarylethylenes,
various
methacrylates,
electrophilic
trapping
reagent
at
terminus
(six‐component
sequential
connection
maximum)
without
any
intermediate
purification
steps.
anionic
flow
system
described
herein
is
active
polymerization,
such
that
styrene
or
methacrylate
can
be
expanded
to
afford
highly
dispersed
oligomers
affecting
other
single
units,
which
means
unequivocal
sequences
were
successfully
inserted
into
internal
terminal
positions.
methodology
provides
adaptable
method
construction
new
molecular
spaces
based
on
unimolecular
control
pinpoint
functionalization.
Macromolecular Rapid Communications,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 13, 2024
A
photo-assisted
process
is
explored
for
improving
the
synthesis
of
oligo(triazole
amide)s,
which
are
prepared
by
solid
phase
using
a
repeated
cycle
two
reactions:
amine-carboxylic
acid
coupling
and
copper-catalyzed
azide-alkyne
cycloaddition
(CuAAC).
The
improvement
second
reaction
investigated
herein.
catalytic
system
involving
Cu(II)Cl
Macromolecular Chemistry and Physics,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 15, 2024
Abstract
This
study
presents
the
exploration
of
sequence‐defined
polyurethanes
(PUs)
as
a
new
class
heteropolymers
capable
precise
conformational
control.
Utilizing
molecular
dynamics
simulations,
folding
behavior
polyurethane
chains
is
investigated
varying
lengths
(11,
20,
and
50
monomers)
in
both
vacuum
aqueous
environments.
The
simulations
reveal
that
heterogeneous
systematically
refold
to
approach
designed
target
structures
better
than
non‐designed
or
with
artificially
disrupted
hydrogen‐bond
networks.
subsequent
synthesis
an
optimized
11‐mer
sequence
(P1)
achieved
through
solid‐phase
chemistry,
thorough
characterization
via
NMR,
MS,
SEC
confirming
accuracy
predicted
its
controlled
chain
length.
Solubility
tests
showed
favorable
results
across
multiple
solvents,
highlighting
versatility
polymer.
research
underscores
potential
emulate
structural
functional
attributes
biological
macromolecules,
opening
pathways
for
their
application
catalysis,
drug
delivery,
advanced
material
design.
findings
illustrate
promising
direction
development
synthetic
polymers
tailored
properties,
emphasizing
transformative
impact
control
polymer
chemistry.
