Self-Cross-Linkable Chitosan-Alginate Complexes Inspired by Mussel Glue Chemistry.

In this study, mussel-inspired chemistry, based on catechol-amine reactions, was adopted to develop self-cross-linkable chitosan-alginate (Chi-Alg) complexes. To do so, the biopolymers were each substituted with ∼20% catechol groups (ChiC and AlgC), and then four complex combinations (Chi-Alg, ChiC-Alg, Chi-AlgC, ChiC-AlgC) were prepared at the surface and in bulk solution. Based on QCM-D and lap shear adhesion tests, the complex with catechol only on Chi (ChiC-Alg) did not show a significant variation from the control complex (Chi-Alg). Conversely, the complexes with catechol on alginate (Chi-AlgC and ChiC-AlgC) rendered a self-cross-linking property and enhanced cohesive properties.

Dopamine-Assisted Layer-by-Layer Deposition Providing Coatings with Controlled Thickness, Roughness, and Functional Properties.

In this study, dopamine-assisted deposition combined with layer-by-layer assembly was investigated as an efficient method for preparing coatings with tunable thickness, roughness, and functional properties. By this method, one can first benefit from the versatile chemistry of dopamine allowing the co-deposition of various functional materials, for example, polymers, ions, and nanoparticles, within the coating. Moreover, the layer-by-layer approach allows tuning the coating thickness and surface roughness, as well as varying the chemical composition of the coating in the vertical direction. Herein, we demonstrated the benefits of using this method in fabricating both single- and multi-component coatings.

Parameterization of the optical constants of polydopamine films for spectroscopic ellipsometry studies.

Bio-inspired polydopamine coatings offer vast possibilities for surface modification of materials. The thickness of such nanometric coatings is usually estimated based on ellipsometry measurements. However, the complex light-absorbing nature of polydopamine is often overlooked when analyzing such data, which can result in inaccurate estimations of the coating thickness as well as the optical properties. In this study, we prepared and characterized three polydopamine coatings where the film thickness and surface roughness are systematically varied. For each case, we developed suitable optical models and showed how an inappropriate optical model can provide inaccurate estimates of the coating properties. AFM height profiles were obtained from scratched areas of each sample to verify the thickness values estimated by ellipsometry. The results confirm that polydopamine coatings, depending on the oxidation conditions, can possess different structural and optical properties, and thus require unique optical models for the ellipsometry analysis.

Cell-imprinted substrates: in search of nanotopographical fingerprints that guide stem cell differentiation.

Cell-imprinted substrates direct stem cell differentiation into various lineages, suggesting the idea of lineage-specific nanotopography. We herein examined the surface topography of five different imprinted cell patterns using AFM imaging and statistical analysis of amplitude, spatial, and hybrid roughness parameters. The results suggest that different cell imprints possess distinguished nanotopographical features.

Water vapor permeation through topical films on a moisture-releasing skin Model.

BACKGROUND: Covering the skin by topical films affects the skin hydration and transepidermal water loss (TEWL). In vivo studies to investigate the water vapor permeation through topical films are complicated, expensive, ethically not preferred, and time- and labor-consuming. The objective of this study was to introduce an in vitro and subject-independent alternative evaluation method to predict the breathability of topical formulations. METHODS: In this study, we developed an in vitro setup to simulate the TEWL values of human skin and investigated the breathability of five polymeric film formers used in topical formulations. Furthermore, a comparative in vivo TEWL study was performed on ten human volunteers with defined areas of skin covered with films of two selected polymers possessing different barrier properties. RESULTS: By employing the in vitro setup, a vinylpyrrolidone/acrylates/lauryl methacrylate copolymer was determined to form the most breathable film, whereas acrylates/octylacrylamide copolymer and shellac films showed the highest barrier properties. The in vivo TEWL study demonstrated the same relative barrier properties for the acrylates/octylacrylamide and polyurethane-64 films, despite a more complex driving force for water vapor permeation due to moisture accumulation on the covered skin surfaces. CONCLUSION: We obtained a good correlation between the in vitro and in vivo results, demonstrating that our model can categorize different polymeric film formers based on their breathability when applied to human skin. This information can aid in selecting suitable film-forming polymers for topical formulations with either breathable or occluding functionalities.

Swelling Behavior, Interaction, and Electrostatic Properties of Chitosan/Alginate Dialdehyde Multilayer Films with Different Outermost Layer.

In this study, self-cross-linked chitosan/alginate dialdehyde multilayer films, capped with either alginate dialdehyde (6 layers) or chitosan (7 layers), were fabricated using the layer-by-layer method. The disruption of the electrostatic equilibrium when exposing the fabricated layers to acidic and alkaline conditions causes swelling within the film and independently in the outermost layer, showing dependence on the ionic strength. Spectroscopic ellipsometry and quartz crystal microbalance with dissipation monitoring were employed to examine the swelling behavior. Atomic force microscopy colloidal probe measurements were conducted to assess the surface forces between the multilayer films at different pH and ionic strengths. Finally, the electrostatic properties of the multilayer films were examined at different pH and ionic strengths using zeta potential measurements. The results suggest that stimuli-responsiveness and overall swelling behavior of the polysaccharide multilayer films significantly depend on the outermost layer, an effect that should expectedly become more pronounced the thinner the film becomes.

Structural Investigation of a Self-Cross-Linked Chitosan/Alginate Dialdehyde Multilayered Film with in Situ QCM-D and Spectroscopic Ellipsometry.

A chitosan/alginate dialdehyde multilayered film was fabricated using the layer-by-layer assembly method. Besides electrostatic interaction that promotes alternate adsorption of the oppositely charged polyelectrolytes, the Schiff base reaction between the amine groups on chitosan and the aldehyde groups on alginate dialdehyde provides a covalently cross-linked film, which after reduction by sodium cyanoborohydride is stable under both acidic and alkaline conditions. Moreover, the cross-linked film is responsive to changes in pH and addition of multivalent salts. The structural properties of the multilayered film such as thickness, refractive index, and water content were examined using simultaneous quartz crystal microbalance with dissipation monitoring and spectroscopic ellipsometry.

PPEGMEMA-based cationic copolymers designed for layer-by-layer assembly.

We have synthesized three PPEGMEMA-based cationic copolymers with similar amine contents but with systematic variation in the average length of the PEG side chains. The positively charged copolymers were paired with alginate to fabricate layer-by-layer assembled multilayered films. It was demonstrated that the polymeric design, in terms of the systematic variation in the average length of the PEG units, affects the polyelectrolyte multilayer growth mechanism and can be used to tune the structural properties and the water content of the layers. In addition, by partial cross-linking of the amine groups present in the copolymer backbone, disintegration of the film induced by pH changes was prevented. Finally, it was demonstrated how the cross-linked multilayered film can exhibit cationic, zwitterionic and anionic properties depending on the pH value and how these changes are associated with swelling, layer contraction and changes in water content.

An engineered cell-imprinted substrate directs osteogenic differentiation in stem cells.

A cell-imprinted poly(dimethylsiloxane)/hydroxyapatite nanocomposite substrate was fabricated to engage topographical, mechanical, and chemical signals to stimulate and boost stem cell osteogenic differentiation. The physicochemical properties of the fabricated substrates, with nanoscale resolution of osteoblast morphology, were probed using a wide range of techniques including scanning electron microscopy, atomic force microscopy, dynamic mechanical thermal analysis, and water contact angle measurements. The osteogenic differentiation capacity of the cultured stem cells on these substrates was probed by alizarin red staining, ALP activity, osteocalcin measurements, and gene expression analysis. The outcomes revealed that the concurrent roles of the surface patterns and viscoelastic properties of the substrate provide the capability of directing stem cell differentiation toward osteogenic phenotypes. Besides the physical and mechanical effects, we found that the chemical signaling of osteoinductive hydroxyapatite nanoparticles, embedded in the nanocomposite substrates, could further improve and optimize stem cell osteogenic differentiation.

Thermo-responsive diblock and triblock cationic copolymers at the silica/aqueous interface: A QCM-D and AFM study.

The properties of synthesized diblock poly(N-isopropylacrylamide)-poly((3-acrylamidopropyl)trimethylammonium chloride) and triblock methoxy-poly(ethylene glycol)-poly(N-isopropylacrylamide)-poly((3-acrylamidopropyl)trimethylammonium chloride) cationic copolymers at the silica/aqueous interface are investigated using quartz crystal microbalance with dissipation monitoring (QCM-D) and atomic force microscopy (AFM). Moreover, dynamic light scattering is employed to assess the copolymers in terms of the hydrodynamic size and interchain aggregation. Although viscoelastic Voigt modeling of the QCM-D data suggests a comparable layer thickness for the copolymers on the silica surface, the AFM imaging and colloidal probe measurements reveal significant differences in surface coverage and thickness of the layers, which are discussed and compared with respect to the stabilization effect by the hydrophilic poly(ethylene glycol) block.

Hofmeister Effect on PNIPAM in Bulk and at an Interface: Surface Partitioning of Weakly Hydrated Anions.

The effect of sodium fluoride, sodium trichloroacetate, and sodium thiocyanate on the stability and conformation of poly(N-isopropylacrylamide), in bulk solution and at the gold-aqueous interface, is investigated by differential scanning calorimetry, dynamic light scattering, quartz crystal microbalance, and atomic force microscopy. The results indicate a surface partitioning of the weakly hydrated anions, i.e., thiocyanate and trichloroacetate, and the findings are discussed in terms of anion-induced electrostatic stabilization. Although attractive polymer-ion interactions are suggested for thiocyanate and trichloroacetate, a salting-out effect is found for sodium trichloroacetate. This apparent contradiction is explained by a combination of previously suggested mechanisms for the salting-out effect by weakly hydrated anions.

Hofmeister effect of salt mixtures on thermo-responsive poly(propylene oxide).

The Hofmeister series is a classification of ions regarding their ability to stabilize or destabilize aqueous solutions of proteins, polymers and other molecules which are partly miscible with water. In this study, we employ differential scanning calorimetry to investigate how the stability of aqueous solutions of poly(propylene oxide) is affected by mixtures of ions with different location in the Hofmeister series. Our results show that the Hofmeister effects of pure salt species are not always linearly additive and that the relative effect of some ions can be reversed depending on the composition of the salt mixture as well as by the absolute and relative concentration of the different species. We suggest that these results can lead to a better understanding of the potential role of the Hofmeister effect in regulation of biological processes, which does always take place in salt mixtures rather than solutions containing just single salt species.