Influence of Sodium Salts on the Swelling and Rheology of Hydrophobically Cross-linked Hydrogels Determined by QCM-D.

Hydrophobically modified copolymers provide a versatile platform of hydrogel materials for diverse applications, but the influence of salts on the swelling and material properties of this class of hydrogels has not been extensively studied. Here, we investigate model hydrogels with three different sodium salts with anions chosen from the classic Hofmeister series to determine how these counterions influence the swelling and mechanical properties of neutral hydrogels. The gel chosen was based on a statistical copolymer of dimethylacrylamide and 2-(N-ethylperfluorooctane sulfonamido) ethyl acrylate (FOSA). Our measurements utilize a quartz crystal microbalance with dissipation (QCM-D) to quantify both swelling and rheological properties of these gels. We find that a 1 mol/L solution of Na2SO4, corresponding to a kosmotropic anion, leads to nearly a 2.6-fold gel deswelling and correspondingly, the complex modulus increases by an order of magnitude under these solution conditions. In contrast, an initial increase in swelling and then a swelling maximum is observed for a 0.02 mol/L concentration in the case of a chaotropic anion, NaClO4, but the changes in the degree of gel swelling in this system are not directly correlated with changes in the gel shear modulus. The addition of NaBr, an anion salt closer to the middle of the chaotropic to kosmotropic range, leads to hydrogel deswelling where the degree of deswelling and the shear modulus are both nearly independent of salt concentration. Overall, the observed trends are broadly consistent with more kosmotropic ions causing diminished solubility ("salting out") and strongly chaotropic ions causing improved solubility ("salting in"), a trend characteristic of the Hoffmeister series governing the solubility of many proteins and synthetic water-soluble polymers, but trends in the shear stiffness with gel swelling are clearly different from those normally observed in chemically cross-linked gels and are correspondingly difficult to interpret. The salt specificity of swelling and mechanical properties of nonionic hydrogels is important for any potential application in which a wide range of salt concentrations and types are encountered.

Mechanically tunable, human mesenchymal stem cell viable poly(ethylene glycol)-oxime hydrogels with invariant precursor composition, concentration, and stoichiometry.

Hydrogels are used widely for exploratory tissue engineering studies. However, currently no hydrogel systems have been reported that exhibit a wide range of elastic modulus without changing precursor concentration, identity, or stoichiometry. Herein, ester and amide-based PEG-oxime hydrogels with tunable moduli (~5-30 kPa) were synthesized with identical precursor mass fraction, stoichiometry, and concentration by varying the pH and buffer concentration of the gelation solution, exploiting the kinetics of oxime bond formation. The observed modulus range can be attributed to increasing amounts of network defects in slower forming gels, as confirmed by equilibrium swelling and small angle neutron scattering (SANS) experiments. Finally, hMSC viability was confirmed in these materials in a 24 h assay. While only an initial demonstration of the potential utility, the controlled variation in defect density and modulus is an important step forward in isolating system variables for hypothesis-driven biological investigations.

Strain rate dependent nanostructure of hydrogels with reversible hydrophobic associations during uniaxial extension.

An energy dissipation mechanism during deformation is required to impart toughness to hydrogels. Here we describe how in situ small angle X-ray scattering (SAXS) provides insight into possible energy dissipation mechanisms for a tough hydrogel based on an amphiphilic copolymer where nanoscale associations of the hydrophobic moieties act as effective crosslinks. The mechanical properties of the hydrogels are intimately coupled with the nanostructure that provides reversible crosslinks and evolves during deformation. As the extension rate increases, more mechanical energy is dissipated from rearrangements of the crosslinks. The scattering is consistent with hopping of hydrophobes between the nanoscale aggregates as the primary rearrangement mechanism. This rearrangement changes the network conformation that leads to non-affine deformation, where the change in the nanostructure dimension from SAXS is less than 15% of the total macroscopic strain. These nanostructure changes are rate dependent and correlated with the relaxation time of the hydrogel. At low strain rate (0.15% s-1), no significant change of the nanostructure was observed, whereas at higher strain rates (1.5% s-1 and 8.4% s-1) significant nanostructure anisotropy occurred during extension. These differences are attributed to the ability for the network chains to rearrange on the time scale of the deformation; when the characteristic time for extension is longer than the average segmental relaxation time, no significant change in nanostructure occurs on uniaxial extension. These results illustrate the importance of strain rate in the mechanical characterization and consideration of relaxation time in the design of tough hydrogels with reversible crosslinks.

Impact of surface wettability on dynamics of supercooled water confined in nitrogen-doped ordered mesoporous carbon.

Confinement of water to nanoscale dimensions enables substantial supercooling through disruption of the hydrogen bonding network. However, there remain questions associated with the importance of the nature of the water-surface interactions relative to physical confinement defined by the pore geometry on the dynamics of supercooled water. Here, a simple route to tune the surface wetting properties through nitrogen doping of carbon is reported. This method leads to nearly indistinguishable mesopore sizes to enable separation of surface wettability and pore size effects. Quasielastic neutron scattering (QENS) is used to probe the proton dynamics of water confined within the mesopores with an average diameter of 4.85 ± 0.05 nm as a function of temperature from 267 K to 189 K. The motions of water in the mesopores follow jump-diffusion. For the temperatures examined, the diffusivity of water in the mesopores decreases with increasing nitrogen doping of the carbon framework. The activation energy associated with proton dynamics increases by approximately 30% with N-doping when compared to the undoped carbon surface, which is attributed to the enhanced surface wettability (favorable interactions between water and pore surface). This acts to provide an energy barrier for the water motions. This work suggests that the influence of surface chemistry on the dynamics of supercooled water confined in mesopores is less than the influence of nanopore size.

Quantitative Rheometry of Thin Soft Materials Using the Quartz Crystal Microbalance with Dissipation.

In the inertial limit, the resonance frequency of the quartz crystal microbalance (QCM) is related to the coupled mass on the quartz sensor through the Sauerbrey expression that relates the mass to the change in resonance frequency. However, when the thickness of the film is sufficiently large, the relationship becomes more complicated and both the frequency and damping of the crystal resonance must be considered. In this regime, a rheological model of the material must be used to accurately extract the adhered film's thickness, shear modulus, and viscoelastic phase angle from the data. In the present work we examine the suitability of two viscoelastic models, a simple Voigt model ( Physica Scripta 1999, 59, 391-396) and a more realistic power-law model ( Langmuir 2015, 31, 4008-4017), to extract the rheological properties of a thermoresponsive hydrogel film. By changing temperature and initial dry film thickness of the gel, the operation of QCM was traversed from the Sauerbrey limit, where viscous losses do not impact the frequency, through the regime where the QCM response is sensitive to viscoelastic properties. The density-shear modulus and the viscoelastic phase angle from the two models are in good agreement when the shear wavelength ratio, d/λ n, is in the range of 0.05-0.20, where d is the film thickness and λ n is the wavelength of the mechanical shear wave at the nth harmonic. We further provide a framework for estimating the physical properties of soft materials in the megahertz regime by using the physical behavior of polyelectrolyte complexes. This provides the user with an approximate range of allowable film thicknesses for accurate viscoelastic analysis with either model, thus enabling better use of the QCM-D in soft materials research.

Rapid assessment of crystal orientation in semi-crystalline polymer films using rotational zone annealing and impact of orientation on mechanical properties.

Crystal orientation in semi-crystalline polymers tends to enhance their performance, such as increased yield strength and modulus, along the orientation direction. Zone annealing (ZA) orients the crystal lamellae through a sharp temperature gradient that effectively directs the crystal growth, but the sweep rate (VZA) of this gradient significantly impacts the extent of crystal orientation. Here, we demonstrate rotational zone annealing (RZA) as an efficient method to elucidate the influence of VZA on the crystal morphology of thin films in a single experiment using isotactic poly(1-butene), PB-1, as a model semi-crystalline polymer. These RZA results are confirmed using standard, serial linear ZA to tune the structure from an almost unidirectional oriented morphology to weakly oriented spherulites. The overall crystallinity is only modestly changed in comparison to isothermal crystallization (maximum of 55% from ZA vs. 48% for isothermal crystallization). However, the average grain size increases and the spherulites become anisotropic from ZA. Due to these structural changes, the Young's modulus of the oriented films, both parallel and perpendicular to the spherulite orientation direction, is significantly increased by ZA. The modulus does become anisotropic after ZA due to the directionality in the crystal structure, with more than a threefold increase in the modulus parallel to the orientation direction for the highest oriented film in comparison to the modulus from isothermal crystallization. RZA enables rapid identification of conditions to maximize orientation of crystals in thin polymer films, which could find utility in determining conditions to improve crystallinity and performance in organic electronics.

Tough Stretchable Physically-Cross-linked Electrospun Hydrogel Fiber Mats.

Nature uses supramolecular interactions and hierarchical structures to produce water-rich materials with combinations of properties that are challenging to obtain in synthetic systems. Here, we demonstrate hierarchical supramolecular hydrogels from electrospun, self-associated copolymers with unprecedented elongation and toughness for high porosity hydrogels. Hydrophobic association of perfluoronated comonomers provides the physical cross-links for these hydrogels based on copolymers of dimethyl acrylamide and 2-(N-ethylperfluorooctane sulfonamido)ethyl methacrylate (FOSM). Intriguingly, the hydrogel fiber mats show an enhancement in toughness in comparison to compression molded bulk hydrogels. This difference is attributed to the size distribution of the hydrophobic aggregates where narrowing the distribution in the electrospun material enhances the toughness of the hydrogel. These hydrogel fiber mats exhibit extensibility more than double that of the bulk hydrogel and a comparable modulus despite the porosity of the fiber mat leading to >25 wt % increase in water content.

Response of Swelling Behavior of Weak Branched Poly(ethylene imine)/Poly(acrylic acid) Polyelectrolyte Multilayers to Thermal Treatment.

Weak polyelectrolyte multilayers (PEMs) prepared by the layer-by-layer technique have attracted a great deal of attention as smart responsive materials for biological and other applications in aqueous medium, but their dynamic behavior as a function of exposure to a wide temperature range is still not well understood. In this work, the thermally dependent swelling behavior of PEMs consisting of branched poly(ethylenimine) and poly(acrylic acid) is studied by temperature controlled in situ spectroscopic ellipsometry. Because of diffusion and interpenetration of polyelectrolytes during film deposition, the PEMs densify with increasing bilayer number, which further affects their water uptake behavior. Upon heating to temperatures below 60 °C, the worsened solvent quality of the PEM in water causes deswelling of the PEMs. However, once heated above this critical temperature, the hydrogen bonds within the PEMs are weakened, which allows for chain rearrangement within the film upon cooling, resulting in enhanced water uptake and increased film thickness. The current work provides fundamental insight into the unique dynamic behavior of weak polyelectrolyte multilayers in water at elevated temperatures.

Supramolecular Hydrophobic Aggregates in Hydrogels Partially Inhibit Ice Formation.

Prevention of ice crystallization is a challenging problem with implications in diverse applications, as well as examining the fundamental low temperature physics of water. Here, we demonstrate a simple route, inspired by water confinement in antifreeze proteins, to inhibit crystallization and provide high water mobility of highly supercooled water using supramolecular hydrogels of copolymers of dimethylacrylamide (DMA) and 2-(N-ethylperfluorooctane sulfonamido)ethyl acrylate (FOSA). These hydrogels can suppress or inhibit freezing of their water, depending on the copolymer composition. Dynamic and static neutron scattering indicate that hydrogels using the copolymer with 22 mol % FOSA partially inhibit ice formation. This behavior is attributed to confinement (<2 nm) of water between the hydrophobic FOSA nanodomains that prevents 45% of the water within the hydrogel from freezing even at 205 K. Very fast dynamics of the amorphous water are observed at 220 K with an effective local diffusivity decreased by only a factor of 2 from that observed at 295 K within the hydrogel using the copolymer with 22 mol % FOSA. The spacing between the hydrophobic nanodomains, tuned through the copolymer composition, appears to modulate the water that can crystallize. These fully hydrated hydrogels (at equilibrium with liquid water at 295 K) can enable a significant fraction of highly supercooled water to be stable down to at least 205 K.

Control of Mesh Size and Modulus by Kinetically Dependent Cross-Linking in Hydrogels.

Kinetically controlled cross-linking processes produce mechanically distinguishable hydrogels using identical precursor chemistry. The oxime ligation demonstrates tunable reaction kinetics with pH and buffer strength, which induce changes in the structural features of hydrogels and determine their mechanical properties. Small-angle neutron scattering and swelling studies provide an insight into how structural properties correlate with mechanical properties for this hydrogel system.

Large-scale solvent driven actuation of polyelectrolyte multilayers based on modulation of dynamic secondary interactions.

Polyelectrolyte multilayers (PEMs), assembled from weak polyelectrolytes, have often been proposed for use as smart or responsive materials. However, such response to chemical stimuli has been limited to aqueous environments with variations in ionic strength or pH. In this work, a large in magnitude and reversible transition in both the swelling/shrinking and the viscoelastic behavior of branched polyethylenimine/poly(acrylic acid) multilayers was realized in response to exposure with various polar organic solvents (e.g., ethanol, dimethyl sulfoxide, and tetrahydrofuran). The swelling of the PEM decreases with an addition of organic content in the organic solvent/water mixture, and the film contracts without dissolution in pure organic solvent. This large response is due to both the change in dielectric constant of the medium surrounding the film as well as an increase in hydrophobic interactions within the film. The deswelling and shrinking behavior in organic solvent significantly enhances its elasticity, resulting in a stepwise transition from an initially liquid-like film swollen in pure water to a rigid solid in pure organic solvents. This unique and recoverable transition in the swelling/shrinking behaviors and the rheological performances of weak polyelectrolyte multilayer film in organic solvents is much larger than changes due to ionic strength or pH, and it enables large scale actuation of a freestanding PEM. The current study opens a critical pathway toward the development of smart artificial materials.

Overcoming confinement limited swelling in hydrogel thin films using supramolecular interactions.

The thin film behavior of poly(N-isopropylacrylamide-stat-2-(N-ethylperfluorooctane sulfonamido)ethyl acrylate) (NIPAAm-stat-FOSA) based hydrogels containing 5 mol% FOSA was elucidated using quartz crystal microbalance with dissipation (QCM-D) in combination with spectroscopic ellipsometry (SE) through examination of the lower critical solution temperature (LCST) and temperature dependent swelling for (dry) thicknesses ranging from 10 nm to 121 nm. For all thin films measured, the LCST was shown to slightly increase (>3 °C) in comparison to that of the bulk sample. However for these films, the increase in LCST was statistically identical, irrespective of thickness. Surprisingly, the volumetric swelling of the hydrogel in thin films, even at temperatures less than the LCST, was similar (within 20%) to the volumetric swelling of the bulk hydrogel, despite the expected significant decrease associated with the hydrogel being constrained by the substrate as predicted by one dimensional Flory-Rehner theory. We attribute this enhancement in swelling compared to theoretical expectations to the ability of the hydrophobic crosslinks to re-arrange under stress, which provides a mechanism to alleviate the decreased dimensionality imposed by the substrate; this mechanism is consistent with a large hysteresis in the swelling when cycling between 35 °C and 5 °C. Unlike the LCST, the swelling ratio increases with decreasing film thickness. At low temperatures (below the LCST), the volume swelling ratio increased from 3.9 to 4.9, while at temperatures above the LCST the swelling ratio increased from 1.5 to 2.5 when the film thickness decreased from 121 nm to 10 nm. The combination of facile processing through solution casting without the need for additional crosslinking chemistry and limited thickness dependent variation of swelling and LCST behavior in these physically crosslinked hydrogels makes these materials attractive for applications requiring thermoresponsive soft coatings.