Polymer brushes provide a new perspective from which to consider the development of energy conversion and storage devices with improved performance and efficiency.

No abstract

The surface properties of soft nanostructured hydrogels are crucial in the design of responsive materials that can be used as platforms to create adaptive devices. The lower critical solution temperature (LCST) of thermo-responsive hydrogels such as poly(N-isopropylacrylamide) (PNIPAm) can be modified by introducing a hydrophilic monomer to create a wide range of thermo-responsive micro-/nano-structures in a large temperature range. Using surface initiation atom-transfer radical polymerization in synthesized anodized aluminum oxide templates, we designed, fabricated, and characterized thermo-responsive nanopillars based on PNIPAm hydrogels with tunable mechanical properties by incorporating acrylamide monomers (AAm). In addition to their LCST, the incorporation of a hydrophilic entity in the nanopillars based on PNIPAm has abruptly changed the topological and mechanical properties of our system. To gain an insight into the mechanical properties of the nanostructure, its hydrophilic/hydrophobic behavior and topological characteristics, atomic force microscopy, molecular dynamics simulations and water contact angle studies were combined. When changing the nanopillar composition, a significant and opposite variation was observed in their mechanical properties. As temperature increased above the LCST, the stiffness of PNIPAm nanopillars, as expected, did so too, in contrast to the stiffness of PNIPAm-AAm nanopillars that decreased significantly. The molecular dynamics simulations proposed a local molecular rearrangement in our nanosystems at the LCST. The local aggregation of NIPAm segments near the center of the nanopillars displaced the hydrophilic AAm units towards the surface of the structure leading to contact with the aqueous environment. This behavior was confirmed via contact angle measurements below and above the LCST.

No abstract

Using a molecular-level equilibrium theory where proteins are described using their crystallographic structure, we have studied protein adsorption from binary and ternary mixtures of myoglobin, lysozyme, and cytochrome c to poly­(methacrylic acid) hydrogel films. The pH gradients these films induce can lead to selective protein adsorption, where the solution pH provides a sensible dial to externally control protein separation. Changing the chemical composition of the polymer network, adding either another acidic or a neutral comonomer, allows for protein localization to controlled spatial regions of the film with nanometer resolution. As pH-sensitive polymer hydrogels are promising candidates for smart, responsive biomaterials, understanding the complexity of competitive protein adsorption is essential. In this work, we highlight the decisive role of amino acid protonation in selective protein adsorption. We present conditions such that the hydrogel film will selectively incorporate the more weakly charged protein, provided that it requires less work to protonate its amino acids.

β-Ketonitrile tautomeric copolymers have demonstrated tunable hydrophilicity/hydrophobicity properties according to surrounding environment, and mechanical properties similar to those of human bone tissue. Both characteristic properties make them promising candidates as biomaterials for bone tissue engineering. Based on this knowledge we have designed two scaffolds based on β-ketonitrile tautomeric copolymers which differ in chemical composition and surface morphology. Two of them were nanostructured, using an anodized aluminum oxide (AAO) template, and the other two obtained by solvent casting methodology. They were used to evaluate the effect of the composition and their structural modifications on the biocompatibility, cytotoxicity and degradation properties. Our results showed that the nanostructured scaffolds exhibited higher degradation rate by macrophages than casted scaffolds (6 and 2.5% of degradation for nanostructured and casted scaffolds, respectively), a degradation rate compatible with bone regeneration times. We also demonstrated that the β-ketonitrile tautomeric based scaffolds supported osteoblastic cell proliferation and differentiation without cytotoxic effects, suggesting that these biomaterials could be useful in the bone tissue engineering field.

No abstract

The use of amphiphilic macrosurfactants as emulsifying agents has shown to have higher efficiency than that of low molecular weight surfactants. Compared to traditional surfactants, polymeric surfactants have lower critical micelle concentrations and lower diffusion coefficients. In this paper, we present a well defined copolymer based on lauryl methacrylate and poly(ethylene glycol) methyl ether methacrylate, prepared by solution radical copolymerization. The product was characterized by NMR and FTIR spectroscopies and the weight-average molecular weight and polydispersity index were analyzed by SEC. The thermal transitions and decomposition temperatures of the copolymers were determined by DSC and TGA, respectively. Due to the hydrophobic and hydrophilic nature of the monomer units, emulsification studies were performed. DLS experiments showed different sizes of the formed micelles depending on solvent polarity due to polymer-polymer or polymer-solvent interactions. Rheological characterization was undertaken to study the viscoelastic properties of the dispersed systems. Finally, two types of experiments to evaluate the polymer abilities as surfactant have been carried out. Firstly, the amphiphilic characteristics of this material allowed the incorporation of small amounts of an organic solvent in water forming only one phase, as well as the incorporation of small amounts of water in the organic solvent forming an emulsified phase. Then, the amphiphilic properties of this macrosurfactant have been fully exploited in order to form highly stable dispersions of carbon nanotubes in water.