7 research outputs found
Heterogeneity and its Influence on the Properties of Difunctional Poly(ethylene glycol) Hydrogels: Structure and Mechanics
Difunctional polymer hydrogels, such
as those prepared from polyÂ(ethylene
glycol) diacrylate (PEGDA) macromers, are widely used for a number
of potential applications in biotechnology and advanced materials
due to their low cost, mild cross-linking conditions, and biocompatibility.
The microstructure of such hydrogels is known to be heterogeneous,
yet little is known about the specific structure itself, how it is
impacted by the molecular parameters of the macromer, or its impact
on macroscopic gel properties. Here, we determine the structure of
PEGDA hydrogels using small-angle neutron scattering over a significant
range of macromer molecular weights and volume fractions. From this,
we propose a structural model for PEGDA hydrogels based on self-excluded,
highly branched star polymers arranged into a fractal network. The
primary implication of this structure is that heterogeneity arises
not from defects in the cross-linking network, as is commonly assumed,
but rather from a heterogeneous distribution of polymer concentration.
This structural model provides a systematic explanation of the linear
elasticity and swelling of PEGDA hydrogels
Decoupling Mechanical and Conductive Dynamics of Polymeric Ionic Liquids via a Trivalent Anion Additive
The mechanical and
conductive properties of a polymeric ionic liquid
(PIL) are decoupled through the addition of a fraction of trivalent
anions to a chloride single-ion conductor. Trivalent phosphate ions
strongly coordinate with polymer-bound imidazoliums, producing an
increase in both the ionic conductivity and the polymer viscosity.
Both the viscosity and the ionic conductivity increase with phosphate
content, and the conductivity is superior to that of the neat PIL
at larger trivalent anion concentrations. The interaggregate spacing
(determined by X-ray scattering), glass transition temperature (measured
by calorimetry), and free volume (estimated by rheology) are each
sensitive to the presence of trivalent ions but not to changes in
the phosphate concentration. Thus, the presence of a fraction of trivalent
anions qualitatively changes the structure and interaction of ions,
resulting in modified macroscopic properties of the PIL. We hypothesize
that this step change in properties upon introducing phosphate ions
is due to a densification of ion aggregates by the trivalent ion,
which strongly binds to imidazolium ions. This provides a new mechanism
for creating PILs with tailored conductive and rheological behavior
Elasticity of Nanoparticles Influences Their Blood Circulation, Phagocytosis, Endocytosis, and Targeting
The impact of physical and chemical modifications of nanoparticles on their biological function has been systemically investigated and exploited to improve their circulation and targeting. However, the impact of nanoparticles’ flexibility (<i>i.e.</i>, elastic modulus) on their function has been explored to a far lesser extent, and the potential benefits of tuning nanoparticle elasticity are not clear. Here, we describe a method to synthesize polyethylene glycol (PEG)-based hydrogel nanoparticles of uniform size (200 nm) with elastic moduli ranging from 0.255 to 3000 kPa. These particles are used to investigate the role of particle elasticity on key functions including blood circulation time, biodistribution, antibody-mediated targeting, endocytosis, and phagocytosis. Our results demonstrate that softer nanoparticles (10 kPa) offer enhanced circulation and subsequently enhanced targeting compared to harder nanoparticles (3000 kPa) <i>in vivo</i>. Furthermore, <i>in vitro</i> experiments show that softer nanoparticles exhibit significantly reduced cellular uptake in immune cells (J774 macrophages), endothelial cells (bEnd.3), and cancer cells (4T1). Tuning nanoparticle elasticity potentially offers a method to improve the biological fate of nanoparticles by offering enhanced circulation, reduced immune system uptake, and improved targeting
Synthesis of Oil-Laden Poly(ethylene glycol) Diacrylate Hydrogel Nanocapsules from Double Nanoemulsions
Multiple emulsions have received
great interest due to their ability
to be used as templates for the production of multicompartment particles
for a variety of applications. However, scaling these complex droplets
to nanoscale dimensions has been a challenge due to limitations on
their fabrication methods. Here, we report the development of oil-in-water-in-oil
(O<sub>1</sub>/W/O<sub>2</sub>) double nanoemulsions <i>via</i> a two-step high-energy method and their use as templates for complex
nanogels comprised of inner oil droplets encapsulated within a hydrogel
matrix. Using a combination of characterization methods, we determine
how the properties of the nanogels are controlled by the size, stability,
internal morphology, and chemical composition of the nanoemulsion
templates from which they are formed. This allows for identification
of compositional and emulsification parameters that can be used to
optimize the size and oil encapsulation efficiency of the nanogels.
Our templating method produces oil-laden nanogels with high oil encapsulation
efficiencies and average diameters of 200–300 nm. In addition,
we demonstrate the versatility of the system by varying the types
of inner oil, the hydrogel chemistry, the amount of inner oil, and
the hydrogel network cross-link density. These nontoxic oil-laden
nanogels have potential applications in food, pharmaceutical, and
cosmetic formulations
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Ion Transport in Dynamic Polymer Networks Based on Metal–Ligand Coordination: Effect of Cross-Linker Concentration
The
development of high-performance ion conducting polymers requires
a comprehensive multiscale understanding of the connection between
ion–polymer associations, ionic conductivity, and polymer mechanics.
We present polymer networks based on dynamic metal–ligand coordination
as model systems to illustrate this relationship. The molecular design
of these materials allows for precise and independent control over
the nature and concentration of ligand and metal, which are molecular
properties critical for bulk ion conduction and polymer mechanics.
The model system investigated, inspired by polymerized ionic liquids,
is composed of polyÂ(ethylene oxide) with tethered imidazole moieties
that facilitate dissociation upon incorporation of nickelÂ(II) bisÂ(trifluoroÂmethylsulfonyl)Âimide.
Nickel–imidazole interactions physically cross-link the polymer,
increase the number of elastically active strands, and dramatically
enhance the modulus. In addition, a maximum in ionic conductivity
is observed due to the competing effects of increasing ion concentration
and decreasing ion mobility upon network formation. The simultaneous
enhancement of conducting and mechanical properties within a specific
concentration regime demonstrates a promising pathway for the development
of mechanically robust ion conducting polymers
Controlling Complex Nanoemulsion Morphology Using Asymmetric Cosurfactants for the Preparation of Polymer Nanocapsules
Complex nanoemulsions,
comprising multiphase nanoscale droplets,
hold considerable potential advantages as vehicles for encapsulation
and delivery as well as templates for nanoparticle synthesis. Although
methods exist to controllably produce complex emulsions on the microscale,
very few methods exist to produce them on the nanoscale. Here, we
examine a recently developed method involving a combination of high-energy
emulsification with conventional cosurfactants to produce oil–water–oil
(O/W/O) complex nanoemulsions. Specifically, we study in detail how
the composition of conventional ethoxylated cosurfactants Span80 and
Tween20 influences the morphology and structure of the resulting complex
nanoemulsions in the water–cyclohexane system. Using a combination
of small-angle neutron scattering and cryo-electron microscopy, we
find that the cosurfactant composition controls the generation of
complex droplet morphologies including core–shell and multicore–shell
O/W/O nanodroplets, resulting in an effective state diagram for the
selection of nanoemulsion morphology. Additionally, the cosurfactant
composition can be used to control the thickness of the water shell
contained within the complex nanodroplets. We hypothesize that this
degree of control, despite the highly nonequilibrium nature of the
nanoemulsions, is ultimately determined by a competition between the
opposing spontaneous curvature of the two cosurfactants, which strongly
influences the interfacial curvature of the nanodroplets as a result
of their ultralow interfacial tension. This is supported by a correlation
between cosurfactant compositions that produces complex nanoemulsions
and those that produce homogeneous mixed micelles in equilibrium surfactant–cyclohexane
solutions. Ultimately, we show that the formation of complex O/W/O
nanoemulsions is weakly perturbed upon the addition of hydrophilic
polymer precursors, facilitating their use as templates for the formation
of polymer nanocapsules
Nucleation under Soft Confinement: Role of Polymer–Solute Interactions
Nucleation of a crystalline phase almost always occurs
at interfaces.
However, the lack of fundamental understanding of the impact of interfacial
properties on nucleation hinders the design of nucleation active materials
for regulating crystallization in practice. In particular, the role
of intermolecular interactions is often neglected in nucleation under
confinement such as those provided by nano- and microporous materials.
Herein, we report the use of a novel material, polymer microgels with
tunable microstructure and chemistry, for understanding the role of
intermolecular interactions in nucleation under confinement and for
controlling crystallization from solution in general. We demonstrate
that by tuning the polymer–solute interactions, solute nucleation
kinetics were promoted by up to 4 orders of magnitude. Moreover, the
effect of polymer–solute interactions was manifested by the
split of nucleation time scales due to the presence of nucleation
sites of distinct chemical compositions in the microgels, characterized
by small angle neutron scattering. Our mechanistic investigations
suggest that the polymer matrix facilitates nucleation by enhancing
effective solute–solute interactions due to solute adsorptive
partitioning and by promoting molecular alignment inferred from preferred
crystal orientations on polymer surfaces. Our results provide new
insights into nucleation at interfaces and help enable a rational
material design approach for directing nucleation of molecular crystals
from solution