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The stability of nonpatterned and nanopatterned strong polyelectrolyte brushes (PEBs) is studied as a function of both brush character and the properties of a contacting liquid. High‐molecular‐weight PEBs of poly(4‐methyl vinylpyridinium iodide) (PMeVP) are synthesized using surface‐initiated radical‐chain polymerization. Nanopatterned brushes (NPBs) line with pattern sizes ranging from 50 to 200 nm are generated by patterning the initiator layer using deep‐ultraviolet photolithography followed by brush growth initiated from the patterned layer. Homogeneous PEBs with different degrees of charging and grafting densities are exposed to water and salt solutions with different temperatures for different periods. The degradation is monitored through dry‐state ellipsometry and atomic force microscopy measurements. Enhanced degrafting for more strongly swollen polymer brushes can be observed in agreement with an "entropic spring" model. Based on the results of the nonpatterned brushes, the NPBs are exposed to water at different temperatures and external salt content for varying periods of time. Counterintuitively, the NPBs show increased degrafting for smaller patterns, which is attributed to different polymer chain dynamics for nanobrushes and microbrushes. We investigate the influence of thermodynamic and kinetic parameters on the stability of (nanopatterned) PEBs and discuss the role of entanglements and formation of complexes in such films. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1283–1295 [ABSTRACT FROM AUTHOR]

The morphology of top-down and bottom-up nanostructured neutral brushes is studied as a function of the production process and the quality of solvent to which the brushes have been exposed. Neutral brushes of poly(tert-butyl methacrylate) (PtBuMA) were grafted from the substrate by surface-initiated radical-chain polymerization (SI-RCP). Brush patterning was conducted using deep ultraviolet (DUV) photolithography following either top-down (TD) or bottom-up (BU) approaches with patterned lines as small as 200 nm. The resulting brushes were immersed in toluene or methanol, and the change of morphology of the dried brushes was monitored using tapping mode atomic force microscopy (AFM). TD nanopatterned brushes (NPBs) exhibit a box-like and BU generated brushes a lens-like shape directly after the production process. We show that the pattern width for the BU brushed depends not only on the wetting properties of the areas adjacent to the pattern but also on the process history to which the sample has been exposed, especially the solvent quality. Furthermore, we show that TD NPBs are cross-linked on the edges of the pattern because of the high-energy process conditions during brush patterning and study the behavior of the thus-obtained structures. [ABSTRACT FROM AUTHOR]

Background: Spider silk is a tear-resistant and elastic biopolymer that has outstanding mechanical properties. Additionally, exiguous immunogenicity is anticipated for spider silks. Therefore, spider silk represents a potential ideal biomaterial for medical applications. All known spider silk proteins, so-called spidroins, reveal a composite nature of silk-specific units, allowing the recombinant production of individual and combined segments. Results: In this report, a miniaturized spidroin gene, named VSO1 that contains repetitive motifs of MaSp1 has been synthesized and combined to form multimers of distinct lengths, which were heterologously expressed as elastin-like peptide (ELP) fusion proteins in tobacco. The elastic penetration moduli of layered proteins were analyzed for different spidroin-based biopolymers. Moreover, we present the first immunological analysis of synthetic spidroin-based biopolymers. Characterization of the binding behavior of the sera after immunization by competitive ELISA suggested that the humoral immune response is mainly directed against the fusion partner ELP. In addition, cytocompatibility studies with murine embryonic fibroblasts indicated that recombinant spidroin-based biopolymers, in solution or as coated proteins, are well tolerated. Conclusion: The results show that spidroin-based biopolymers can induce humoral immune responses that are dependent on the fusion partner and the overall protein structure. Furthermore, cytocompatibility assays gave no indication of spidroin-derived cytotoxicity, suggesting that recombinant produced biopolymers composed of spider silk-like repetitive elements are suitable for biomedical applications. [ABSTRACT FROM AUTHOR]

In the last two decades it was shown that plants have a great potential for production of specific heterologous proteins. But high cost and inefficient downstream processing are a main technical bottleneck for the broader use of plant-based production technology especially for protein-based products, for technical use as fibres or biodegradable plastics and also for medical applications. High-performance fibres from recombinant spider silks are, therefore, a prominent example. Spiders developed rather different silk materials that are based on proteins. These spider silks show excellent properties in terms of elasticity and toughness. Natural spider silk proteins have a very high molecular weight, and it is precisely this property which is thought to give them their strength. Transgenic plants were generated to produce ELPylated recombinant spider silk derivatives. These fusion proteins were purified by Inverse Transition Cycling ( ITC) and enzymatically multimerized with transglutaminase in vitro. Layers produced by casting monomers and multimers were characterized using atomic force microscopy ( AFM) and AFM-based nanoindentation. The layered multimers formed by mixing lysine- and glutamine-tagged monomers were associated with the highest elastic penetration modulus. [ABSTRACT FROM AUTHOR]