Probing gels and emulsions using large-amplitude oscillatory shear and frictional studies with soft substrate skin surrogates.

Water swellable crosslinked polymers are widely used in oil-in-water emulsions for the healthcare and cosmetic industries due to their thickening properties. In this study, we investigate the rheological and lubrication behavior of a microgel-forming polymer, a lightly-crosslinked hydrophobically modified polyacrylic acid (HMPAA), in an aqueous medium and in an emulsion. Hydrogenated phosphatidylcholine, a class of phospholipids, is used as a surfactant in the emulsions composed of different oil content. Rheological behavior is probed both in the linear and non-linear regimes using small strain amplitude and large amplitude oscillatory shear (LAOS) experiments, respectively. We observe all systems to exhibit gel-like behavior with the elastic modulus (G') dominating and being frequency independent. Lissajous-Bowditch plots and nonlinear parameters obtained under large deformation show that the emulsions can resist greater deformations with smaller increase in the viscous dissipation when compared to a HMPAA gel. For tribology experiments, friction curves in a range of entrainment speeds are examined using substrates to mimic the skin surface (PDMS and Bioskin®). The role of polymer hydrophobicity on the different substrates are also explored by comparing the behavior of HMPAA to that of its hydrophilic analog, a polyacrylic acid highly crosslinked. We find the friction coefficient to be dependent on the hydrophobicity of the substrate and the polymer as well as the substrate roughness. These results taken together provide insights in the formulation of skincare products with efficient lubrication properties for different skin characteristics.

Linking polymer hydrophobicity and molecular interactions to rheology and tribology in phospholipid-containing complex gels.

HYPOTHESIS: The rheological behavior and frictional properties (macroscopic level) of systems containing a hydrophobically modified polymer and phospholipids depend on the hydrophobic association that occur between the hydrophobic moiety of the polymer and the phospholipid tails (molecular level). The hydrophobicity of the polymer can thus be used to control its interactions with phospholipids, and manipulate complex gel macroscopic behavior. EXPERIMENTS: By using systems composed of a crosslinked hydrophobically modified polyacrylic acid (HMPAA) or a crosslinked polyacrylic acid polymer (PAA) and phospholipids, we examine the underlying mechanisms through which the components interact using isothermal titration calorimetry (ITC) and their effect on rheological and tribological characteristics of complex gels. FINDINGS: We find the systems containing HMPAA and phospholipid exhibit gel-like behavior with the elastic modulus increasing substantially upon phospholipid addition due to hydrophobic interactions that result in a more interconnected network formation, as evidenced by ITC measurements. Similar experiments with a crosslinked polyacrylic acid polymer (PAA) show no interactions, lending credence to our hypothesis. In addition, soft tribological behavior shows lower friction coefficients at low entrainment speeds with HMPAA concentration and the addition of phospholipid, while no change in friction coefficient was observed in the case of increasing PAA concentration, indicating HMPAA and phospholipids to be interacting with the soft PDMS contacts.

Recent advances in biodegradable matrices for active ingredient release in crop protection: Towards attaining sustainability in agriculture.

Climate changes, emerging species of plant pests, and deficits of clean water and arable land have made availability of food to the ever-increasing global population a challenge. Excessive use of synthetic pesticides to meet ever-increasing production needs has resulted in development of resistance in pest populations, as well as significant ecotoxicity, which has directly and indirectly impacted all life-forms on earth. To meet the goal of providing safe, sufficient, and high-quality food globally with minimal environmental impact, one strategy is to focus on targeted delivery of pesticides using eco-friendly and biodegradable carriers that are derived from naturally available materials. Herein, we discuss some of the recent approaches to use biodegradable matrices in crop protection, while exploring their design and efficiency. We summarize by discussing associated challenges with the existing approaches and future trends that can lead the world to more sustainable agricultural practices.

Nanodiamond-stabilized Pickering emulsions: Microstructure and rheology.

HYPOTHESIS: We envisage the use of hydroxylated detonation nanodiamonds (ND-OH), a relatively novel carbonaceous filler with high adsorption activity, small size, and large surface area to create Pickering emulsions. The emulsion behavior under shear and the extent to which the microstructure can rebuild after breakdown is dependent on its yield stress. EXPERIMENTS: Using a model system consisting of isopropyl palmitate and water stabilized by ND-OH particles, we investigate the stability of these emulsions, their microstructure and rheological behavior as a function of ND-OH concentration. FINDINGS: Confocal microscopy reveals that increasing ND-OH concentration results in smaller droplet sizes in the emulsions. This behavior is consistent with our rheological results of higher elastic modulus G' and yield stress of the emulsion with increased ND-OH, as the presence of smaller droplets facilitates the formation of a densely packed network. We find the rheological behavior of these emulsions to be a hybrid of colloidal gels and surfactant-stabilized emulsions, with interparticle interactions and droplets deformability dictating their elasticity and yield stress behavior. Structure recovery following large shear reveals the degree of microstructure recovery to depend on the applied stress, with the recovered modulus collapsing into a single master-curve when the applied stress is scaled by the yield stress.

Fabrication of Guar-Only Electrospun Nanofibers by Exploiting a High- and Low-Molecular Weight Blend.

We present a facile approach to electrospin nanofibers of guar galactomannan by blending high- and low-molecular weights (MWs) of guar. We discover that while neither native high MW guar nor hydrolyzed low MW guar is electrospinnable on its own, their combination leads to synergism in producing defect-free nanofibers. Such an approach of fabricating nanofibers from blending multiple MWs of the same polymer may provide an easy route to produce nanofibers of biopolymers which are typically hard to electrospin. Rheological studies reveal that a limiting amount of native guar is needed for electrospinnability, and for those systems that have the proportionate amount of native guar, there is a critical total concentration above which fibers form. Interestingly, a plot of blend viscosity versus guar concentration reveals two power-law regimes with an inflection point, above which fiber formation can be achieved akin to the behavior observed for pure (i.e., nonblend) polymers.