Evidence is shown that cosolvent mixtures control the coacervation of mixtures of oppositely charged polyelectrolytes. Binary and ternary solvent mixtures lead to non-monotonic solubility as a function of the average dielectric constants of the solvent mixtures. These data are rationalized by considering both electrostatic-driven phase separation and solvophobic-driven phase separation using group contribution effects on solubility parameters.
View Article and Find Full Text PDFA model zwitterionic polysulfobetaine, poly(3-(acrylamidopropyl-dimethyl-ammonium) propyl-1-sulfonate) (pAPAPS), phase separates upon cooling and exhibits an upper critical solution temperature (UCST) behavior with no added salt in deuterium oxide solutions. Dynamic light scattering measurements indicate the presence of distinct fast and slow diffusive modes, where the fast mode is interpreted as a collective diffusion coefficient and the slow mode is attributed to the diffusion of multi-chain dynamic clusters. The relative population of fast and slow modes varies systematically with temperature and concentration.
View Article and Find Full Text PDFWe examine whether the mode-coupling theory of Kawasaki and Ferrell (KF) [Kawasaki, K. Kinetic Equations and Time Correlation Functions of Critical Fluctuations. 1970, 61 (1), 1-56; Ferrell, R.
View Article and Find Full Text PDFThis paper focuses on how to identify normal, derated power and abnormal data in operation data, which is key to intelligent operation and maintenance applications such as wind turbine condition diagnosis and performance evaluation. Existing identification methods can distinguish normal data from the original data, but usually remove power curtailment data as outliers. A multi-Gaussian-discrete probability distribution model was used to characterize the joint probability distribution of wind speed and power from wind turbine SCADA data, taking the derated power of the wind turbine as a hidden random variable.
View Article and Find Full Text PDFNanostructures similar to those found in the vividly blue wings of Morpho butterflies and colorful photonic crystals enable structural color through constructive interference of light waves. Different from commonly studied structure-colored materials using periodic structures to manipulate optical properties, we report a previously unrecognized approach to precisely control the structural color and light transmission via a novel photonic colloidal gel without long-range order. Nanoparticles in this gel form micrometer-sized bicontinuous domains driven by the microphase separation of binary solvents.
View Article and Find Full Text PDFResponsive polyzwitterionic materials have become important for a range of applications such as environmental remediation and targeted drug delivery. Much is known about the macroscopic phase-behaviors of such materials, but how the smaller scale single-chain structures of polyzwitterions respond to external stimuli is not well understood, especially at temperatures close to their phase boundaries. Such chain conformation responses are important in directing larger-scale associative properties.
View Article and Find Full Text PDFA synthetic strategy yielded polyelectrolytes and polyampholytes with tunable net charge for complexation and protein binding. Organocatalytic ring-opening polymerizations yielded aliphatic polycarbonates that were functionalized with both carboxylate and ammonium side chains in a post-polymerization, radical-mediated thiol-ene reaction. Incorporating net charge into the polymer architecture altered the chain dimensions in phosphate buffered solution in a manner consistent with self-complexation and complexation behavior with model proteins.
View Article and Find Full Text PDFThe interfacial tension of coacervates, the liquidlike phase composed of oppositely charged polymers that coexists at equilibrium with a supernatant, forms the basis for multiple technologies. Here we present a comprehensive set of experiments and molecular dynamics simulations to probe the effect of molecular mass on interfacial tension γ, far from the critical point, and derive γ=γ_{∞}(1-h/N), where N is the degree of polymerization, γ_{∞} is the infinite molecular mass limit, and h is a constant that physically corresponds to the number of monomers of one chain within the coacervate correlation volume.
View Article and Find Full Text PDFAssociating soft matter such as surfactants, polymers, proteins, and liposomes, may form structures with dimensions not readily accessible by optical methods. Scattering methods can provide detailed information about the mechanism of associative phase separation including nucleation density, size, and shape. Ultra-small angle neutron scattering, a reciprocal space method, provides sensitivity to submicron to micron-scale structures in a non-invasive manner and described in the context of nucleation and growth of dilute droplets formed by a temperature jump into the meta-stable region of polyelectrolyte complex coacervates.
View Article and Find Full Text PDFSupramolecular chemistry has provided versatile and affordable solutions for the design of tough, flexible polymers. However, application of supramolecular chemistry has been limited to the production of rigid, high-performance polymers due to weak segment mobility. This paper describes a new method of toughening rigid high-performance polymers using the synergistic effect between dual Cu -coordination bonds as a crosslink.
View Article and Find Full Text PDFWe described a new concept for the design of high-performance supramolecular thermosets by incorporating point-face cation-π interactions in covalently crosslinked networks. Our findings showed an unprecedented increase in tensile strength and extensibility at once, a previously unknown behavior for stiff high performance polymers.
View Article and Find Full Text PDFChem Commun (Camb)
September 2019
A cation-π induced lithium-doped conjugated microporous polymer, Li+-PTAT, was constructed. It was proved that the point to face cation-π interactions between Li+ and indole can endow the resulting Li+-PTAT with high Li+ content and without agglomeration, which further leads to its encouraging hydrogen storage capacity.
View Article and Find Full Text PDFA new type of carboxylic-functional indole-based aerogel (CHIFA) has been successfully prepared a facile sol-gel technology, which possessed a highly effective removal of heavy metals from aqueous solution through the synergistic effects of face-point and point-point interactions.
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