Effect of Polymer Gel Elasticity on Complex Coacervate Phase Behavior.

Gels are key materials in biological systems such as tissues and may control biocondensate formation and structure. To further understand the effects of elastic environments on biomacromolecular assembly, we have investigated the phase behavior and radii of complex coacervate droplets in polyacrylamide (PAM) networks as a function of gel modulus. Poly-l-lysine (PLL) and sodium hyaluronate (HA) complex coacervate phases were prepared in PAM gels with moduli varying from 0.035 to 15.0 kPa. The size of the complex coacervate droplets is reported from bright-field microscopy and confocal fluorescence microscopy. Overall, the complex coacervate droplet volume decreases inversely with the modulus. Fluorescence microscopy is also used to determine the phase behavior and concentration of fluorescently tagged HA in the complex coacervate phases as a function of ionic strength (100-270 mM). We find that the critical ionic strength and complex coacervate stability are nonmonotonic as a function of the network modulus and that the local gel concentration can be used to control phase behavior and complex coacervate droplet size scale. By understanding how elastic environments influence simple electrostatic assembly, we can further understand how biomacromolecules exist in complex, crowded, and elastic cellular environments.

Ionic environment effects on collagen type II persistence length and assembly.

Collagen type II is a main structural protein in cartilage and forms fibrils. The radius of the fibrils ranges from 50 nm to a few hundred nm, and previous theoretical studies point to electrostatics and collagen elasticity (measured as the persistence length, lp) as the main origin for the self-limiting size scales. In this study, we have investigated the collagen triple helical structure and fibril size scales in pH 2 solutions with varying NaCl concentrations from 10-4 to 100 mM, at which collagen is positively charged, and in pH 7.4 solutions, with varying ionic strengths from 100 to 250 mM, at which collagen is both positively and negatively charged. Using static and dynamic light scattering, the radius of gyration (Rg), hydrodynamic radius (Rh), and second virial coefficient (A2) of collagen triple helices are determined, and lp is calculated. With increasing ionic strength, triple helical lp decreases in pH 2 solutions and increases in pH 7.4 solutions. The value ranges from 60 to 100 nm depending on the ionic environment, but at the salt concentration at which A2 is near zero, there are no net backbone interactions in solution, and the intrinsic collagen triple helix lp is determined to be 90-95 nm. Electron microscopy is used to determine the diameter of fibrils assembled in pH 7.4 conditions, and we compare lp of the collagen triple helices and fibril diameter using recent theory on fibril assembly. By better understanding collagen lp and fibril assembly, we can further understand mechanisms of biomacromolecule self-assembly.

Persistence length of α-helical poly-L-lysine.

The α-helix has a significant role in protein function and structure because of its rigidity. In this study, we investigate the persistence length, lp, of α-helical poly-L-lysine, PLL, for two molecular weights. PLL experiences a random coil-helix transition as the pH is raised from 7 to 12. Using light scattering experiments to determine the radius of gyration (Rg), hydrodynamic radius, (Rh), the shape factor (Rg/Rh), and second virial coefficient (A2), and circular dichroism to determine the helical content, we find the structure and lp of PLL as a function of pH (7.4-11.4) and ionic strength (100-166 mM). With increasing pH, we find an increase in lp from 2 nm to 15-21 nm because of α-helix formation. We performed dissipative particle dynamics (DPD) simulations and found a similar increase in lp. While this lp is less than that predicted by molecular dynamics simulations, it is consistent with other experimental results, which quantify the mechanics of α-helices. By determining the mechanics of helical polypeptides like PLL, we can further understand their implications to protein function.

High Modulus, Thermally Stable, and Self-Extinguishing Aramid Nanofiber Separators.

Mechanically and thermally robust separators offer an alternative approach for preventing battery failure under extreme conditions such as high loads and temperatures. However, the trade-off between electrochemical performance and mechanical and thermal stability remains an ongoing challenge. Here, we investigate aramid nanofiber (ANF) separators that possess high moduli and self-extinguishing characteristics. The ANF separators are formed from the dissolution of bulk Kevlar fibers and their subsequent vacuum-assisted self-assembly. Thermogravimetric analysis shows a high 5 wt % decomposition temperature of 447 °C, which is over ∼175 °C higher than commercial Celgard separators. The ANF separator also possesses a high Young's modulus of 8.8 GPa, which is ∼1000% higher than commercial separators. Even when dry or when soaked in battery electrolyte, the ANF separators self-extinguish upon exposure to flame, whereas commercial separators melt or drip. We show that these features, although adventitious, present a trade-off with electrochemical performance in which a lithium nickel manganse cobalt (NMC) oxide-based battery possessed a reduced capacity of 123.4 mA h g-1. Considering the separator holistically, we propose that the ANF separator shows an excellent balance of the combined properties of high modulus, flame-resistance, thermal stability, and electrochemical stability and might be suitable for extreme environment applications with further testing.

Comparison of KBr and NaCl effects on the glass transition temperature of hydrated layer-by-layer assemblies.

The influence of assembly and post-assembly conditions on the glass transition temperature of free-standing poly(diallyldimethyl ammonium) (PDADMA)/poly(4-styrene sulfonate) (PSS) layer-by-layer (LbL) films assembled in 0.5M NaCl and 0.5M KBr are explored using modulated differential scanning calorimetry. Upon completion, PDADMA/PSS LbL assemblies are hydrated using solutions containing various concentrations of KBr. The data indicate that water provides the primary driving force for changes in the glass transition temperature of completed films rather than the post-assembly salt type. However, upon changing the assembly salt conditions from NaCl to KBr, the glass transition temperature shows a decrease of nearly 20 °C. Additionally, the composition of the films upon analysis with 1H NMR spectroscopy and neutron activation analysis indicates an elevated number of extrinsic binding sites within the film structure when KBr is the assembly salt. This shows a clear link between the assembly conditions and the internal structure and, therefore, the thermal properties of PDADMA/PSS LbL assemblies.

QCM-D Investigation of Swelling Behavior of Layer-by-Layer Thin Films upon Exposure to Monovalent Ions.

Polyelectrolyte multilayers and layer-by-layer assemblies are susceptible to structural changes in response to ionic environment. By altering the salt type and ionic strength, structural changes can be induced by disruption of intrinsically bound ion pairs within the multilayer network via electrostatic screening. Notably, high salt concentrations have been used for the purposes of salt-annealing and self-healing of LbL assemblies with KBr, in particular, yielding a remarkably rapid response. However, to date, the structural and swelling effects of various monovalent ion species on the behavior of LbL assemblies remain unclear, including a quantitative view of ion content in the LbL assembly and thickness changes over a wide concentration window. Here, we investigate the effects of various concentrations of KBr (0 to 1.6 M) on the swelling and de-swelling of LbL assemblies formed from poly(diallyldimethylammonium) polycation (PDADMA) and poly(styrene sulfonate) polyanion (PSS) in 0.5 M NaCl using quartz-crystal microbalance with dissipation (QCM-D) monitoring as compared to KCl, NaBr, and NaCl. The ion content after salt exchange is quantified using neutron activation analysis (NAA). Our results demonstrate that Br- ions have a much greater effect on the structure of as-prepared thin films than Cl- at ionic strengths above assembly conditions, which is possibly caused by the more chaotropic nature of Br-. It is also found that the anion in general dominates the swelling response as compared to the cation because of the excess PDADMA in the multilayer. Four response regimes are identified that delineate swelling due to electrostatic repulsion, slight contraction, swelling due to doping, and film destruction as ionic strength increases. This understanding is critical if such materials are to be used in applications requiring submersion in chemically dynamic environments such as sensors, coatings on biomedical implants, and filtration membranes.