This work explored solution properties of linear and star poly(methacrylic acids) with four, six, and eight arms (PMAA, 4PMAA, PMAA, and 8PMAA, respectively) of matched molecular weights in a wide range of pH, salt, and polymer concentrations. Experimental measurements of self-diffusion were performed by fluorescence correlation spectroscopy (FCS), and the results were interpreted using the scaling theory of polyelectrolyte solutions. While all PMAAs were pH sensitive and showed an increase in hydrodynamic radius ( ) with pH in the dilute regime, the of star polymers (measured at basic pH values) was significantly smaller for the star polyacids due to their more compact structure.
View Article and Find Full Text PDFThe intrinsic reversibility of dynamic covalent bonding, such as the furan-maleimide Diels-Alder (DA) cycloaddition reactions, enables reprocessable, self-healing polymer materials that can be reconfigured via the mechanism of solid-state plasticity. In this work, the temperature-dependent exchange rates of stereochemically distinct endo and exo DA bonds are leveraged to achieve tunable, temperature- and stress-activated shape morphing in Diels-Alder polymer (DAP) networks. Through thermal annealing, ≈35% of endo DA isomers are converted in neat DAP networks to the thermodynamically favored exo form, achieving ≈97% exo after complete annealing at 60 °C.
View Article and Find Full Text PDFThe extracellular matrix of most bacterial biofilms contains polysaccharides, proteins, and nucleic acids. These biopolymers have been shown to mediate fundamental biofilm-related phenotypes including surface attachment, intercellular adhesion, and biocide resistance. Enzymes that degrade polymeric biofilm matrix components, including glycoside hydrolases, proteases, and nucleases, are useful tools for studying the structure and function of biofilm matrix components and are also being investigated as potential antibiofilm agents for clinical use.
View Article and Find Full Text PDFOne of the challenges preventing wide use of inorganic salt hydrate phase change materials (PCMs) is their low viscosity above their melting point, leading to leakage, phase segregation, and separation from heat exchanger surfaces in thermal management applications. The development of a broad strategy for using polymers that provide tunable, temperature-reversible shape stabilization of a variety of salt hydrates by using the lowest possible polymer concentrations is hindered by differences in solubility and gelation behavior of polymers with change in the type of ion. This work addressed the challenge of creating robust, temperature-responsive shape-stabilizing polymer gels (i.
View Article and Find Full Text PDFDespite the potential use of polyelectrolyte multilayers for biomedical, separation, and energy applications, their dynamic properties are not sufficiently understood. In this work, center-of-mass diffusion of a weak polyacid-poly(methacrylic acid) (PMAA) of linear and 8-arm architecture (L-PMAA and 8-PMAA, respectively) and matched molecular weight-was studied in layer-by-layer (LbL) assemblies with poly(diallyldimethylammonium) chloride (PDADMAC) of varied molecular weight. The film deposition at low-salt, acidic conditions when PMAA was only partially ionized yielded thicker, more diffused layers with shorter PDADMAC chains, and bilayer thickness decreased for multilayers constructed with longer PDADMAC.
View Article and Find Full Text PDF