Polyelectrolyte complexes are a fascinating class of soft materials that can span the full spectrum of mechanical properties from low-viscosity fluids to glassy solids. This spectrum can be accessed by modulating the extent of electrostatic association in these complexes. However, to realize the full potential of polyelectrolyte complexes as functional materials, their molecular level details need to be clearly correlated with their mechanical response. The present work demonstrates that by making simple amendments to the chain architecture, it is possible to affect the salt responsiveness of polyelectrolyte complexes in a systematic manner. This is achieved by quaternizing poly(4-vinylpyridine) (QVP) with methyl, ethyl, and propyl substituentsthereby increasing the hydrophobicity with increasing side chain lengthand complexing them with a common anionic polyelectrolyte, poly(styrenesulfonate). The mechanical behavior of these complexes is compared to the more hydrophilic system of poly(styrenesulfonate) and poly(diallyldimethylammonium) by quantifying the swelling behavior in response to salt stimuli. More hydrophobic complexes are found to be more resistant to doping by salt, yet the mechanical properties of the complex remain contingent on the overall swelling ratio of the complex itself, following near universal swelling–modulus master curves that are quantified in this work. The rheological behaviors of QVP complex coacervates are found to be approximately the same, only requiring higher salt concentrations to overcome strong hydrophobic interactions, demonstrating that hydrophobicity can be used as an important parameter for tuning the stability of polyelectrolyte complexes in general, while still preserving the ability to be processed “saloplastically”.
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 n th 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.
High-flux filtration membranes constructed through scalable and sustainable methods are desirable for energy-efficient separations. Often, these criteria are difficult to be reconciled with one another. Polymeric membranes can provide high flux but frequently involve organic solvents in processing steps. Solubility of many polymeric membranes in organic media also restricts their implementation in solvent filtration. In the present work, we report a simple and high-throughput aqueous processing approach for polyelectrolyte complex (PEC) membranes with controllable porosity and stability in various aqueous and organic environments. PECs are materials composed of oppositely charged polymer chains that can form solids in aqueous environments, yet which can be dissolved in very specific salt solutions capable of breaking the interpolymer ion pairs. By exploiting the salt-induced dissolution and subsequent reformation of the complex, nano- to microporous films are rapidly synthesized which resemble membranes obtained through conventional solvent-phase inversion techniques. PECs remain stable in organic solvents because of the low dielectric constant of the environment, which enhances electrostatic interactions, making them suitable for a wide range of water and solvent filtration applications. Here, we elucidate how the polymer-phase behavior can be manipulated to exercise morphological control, test membrane performance for water and solvent filtration, and quantify the mechanical stability of PECs in relevant conditions.
Quantitatively understanding the self-assembly of amphiphilic macromolecules at liquid–liquid interfaces is a fundamental scientific concern due to its relevance to a broad range of applications including bottom-up nanopatterning, protein encapsulation, oil recovery, drug delivery, and other technologies. Elucidating the mechanisms that drive assembly of amphiphilic macromolecules at liquid–liquid interfaces is challenging due to the combination of hydrophobic, hydrophilic, and Coulomb interactions, which require consideration of the dielectric mismatch, solvation effects, ionic correlations, and entropic factors. Here we investigate the self-assembly of a model block copolymer with various charge fractions at the chloroform–water interface. We analyze the adsorption and conformation of poly(styrene)- block -poly(2-vinylpyridine) (PS- b -P2VP) and of the homopolymer poly(2-vinylpyridine) (P2VP) with varying charge fraction, which is controlled via a quaternization reaction and distributed randomly along the backbone. Interfacial tension measurements show that the polymer adsorption increases only marginally at low charge fractions (<5%) but increases more significantly at higher charge fractions for the copolymer, while the corresponding randomly charged P2VP homopolymer analogues display much more sensitivity to the presence of charged groups. Molecular dynamics (MD) simulations of the experimental systems reveal that the diblock copolymer (PS- b -P2VP) interfacial activity could be mediated by the formation of a rich set of complex interfacial copolymer aggregates. Circular domains to elongated stripes are observed in the simulations at the water–chloroform interface as the charge fraction increases. These structures are shown to resemble the spherical and cylindrical helicoid structures observed in bulk chloroform as the charge fraction increases. The self-assembly of charge-containing copolymers is found to be driven by the association of the charged component in the hydrophilic block, with the hydrophobic segments extending away from the hydrophilic cores into the chloroform phase.
Guanidinium is one of nature's strongest denaturants and is also a motif that appears in several interfacial contexts such as the RGD sequence involved in cell adhesion, cell penetrating peptides, and antimicrobial molecules. It is important to quantify the origin of guanidinium's ion-specific interactions so that its unique behavior may be exploited in synthetic applications. The present work demonstrates that guanidinium ions can both break and form strongly associating ion complexes in a context-dependent way. These insights into guanidinium's behavior are elucidated using polyelectrolyte complexes (PECs), where interpolymer ion pairs between oppositely charged polymers play an important role in determining material stability. Different polycation−polyanion combinations can span a large range of association affinities, where more strongly associating complexes can remain insoluble in concentrated salt solutions and in extreme pH conditions. This high stability is desirable in several application contexts for PECs, but also renders them challenging to process and, therefore, to study since they cannot be dissolved into polymer solutions. Here we demonstrate that guanidinium salts are very effective in dissolving the poly(styrenesulfonate)/poly(allylamine) (PSS:PAH) complex, which has one of the highest reported polycation−polyanion association affinities. We also demonstrate the importance of charge identity in complexation phenomena by functionalizing guanidinium directly into poly(allylamine), resulting in a complex that remains stable under highly denaturing conditions. The model system of PSS:PAH is used to glean insights into guanidinium's denaturing activity, as well as to broadly comment on the nature of ion-specific interactions in charged macromolecules.
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