Cross-Linking of a Hydrophilic, Antimicrobial Polycation toward a Fast-Swelling, Antimicrobial Superabsorber and Interpenetrating Hydrogel Networks with Long Lasting Antimicrobial Properties.

A hemocompatible, antimicrobial 3,4en-ionene (PBI) derived by polyaddition of trans-1,4-dibromo-2-butene and N,N,N',N'-tetramethyl-1,3-propanediamine was cross-linked via its bromine end groups using tris(2-aminoethyl)amine (TREN) to form a fast-swelling, antimicrobial superabsorber. This superabsorber is taking up the 30-fold of its weight in 60 s and the granulated material is taking up 96-fold of its weight forming a hydrogel. It fully prevents growth of the bacterium Staphylococcus aureus. The PBI network was swollen with 2-hydroxyethyl acrylate and glycerol dimethacrylate followed by photopolymerization to form an interpenetrating hydrogel (IPH) with varying PBI content in the range of 2.0 to 7.8 wt %. The nanophasic structure of the IPH was confirmed by atomic force microscopy and transmission electron microscopy. The bacterial cells of the nosocomial strains Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa are killed on the IPH even at the lowest PBI concentration. The antimicrobial activity was retained after washing the hydrogels for up to 4 weeks. The IPHs show minor leaching of PBI far below its antimicrobial active concentration using a new quantitative test for PBI detection in solution. This leaching was shown to be insufficient to form an inhibition zone and killing bacterial cells in the surroundings of the IPH.

Enzymatic mineralization generates ultrastiff and tough hydrogels with tunable mechanics.

The cartilage and skin of animals, which are made up of more than fifty per cent water, are rather stiff (having elastic moduli of up to 100 megapascals) as well as tough and hard to break (with fracture energies of up to 9,000 joules per square metre). Such features make these biological materials mechanically superior to existing synthetic hydrogels. Lately, progress has been made in synthesizing tough hydrogels, with double-network hydrogels achieving the toughness of skin and inorganic-organic composites showing even better performance. However, these materials owe their toughness to high stretchability; in terms of stiffness, synthetic hydrogels cannot compete with their natural counterparts, with the best examples having elastic moduli of just 10 megapascals or less. Previously, we described the enzyme-induced precipitation and crystallization of hydrogels containing calcium carbonate, but the resulting materials were brittle. Here we report the enzyme-induced formation of amorphous calcium phosphate nanostructures that are homogenously distributed within polymer hydrogels. Our best materials have fracture energies of 1,300 joules per square metre even in their fully water-swollen state-a value superior to that of most known water-swollen synthetic materials. We are also able to modulate their stiffness up to 440 megapascals, well beyond that of cartilage and skin. Furthermore, the highly filled composite materials can be designed to be optically transparent and to retain most of their stretchability even when notched. We show that percolation drives the mechanical properties, particularly the high stiffness, of our uniformly mineralized hydrogels.

Urease-induced calcification of segmented polymer hydrogels - a step towards artificial biomineralization.

Natural organic/inorganic composites, such as nacre, bones and teeth, are perfectly designed materials with exceptional mechanical properties. Numerous approaches have been taken to synthetically prepare such composites. The presented work describes a new way of mineralizing bulk materials on a large scale following the approach of bioinduced mineralization. To this end, a series of polymer conetworks with entrapped urease were prepared. After polymerization, the entrapped urease shows high enzymatic activity. The bioactive polymer conetworks were then treated with an aqueous mixture of urea and CaCl2. The urease-induced calcification indeed allows formation of carbonate crystals exclusively within the hydrogel even at room temperature. The influence of network composition, degree of cross-linking, immobilized urease concentration and temperature of calcification were investigated. By varying these parameters, spherical, monolithic clusters, as well as bar-like nanocrystals with different aspect ratios in spherical or dendritic arrays, are formed. The grown nanocrystals improve the stiffness of the starting material by up to 700-fold, provided that the microstructure shows a dense construction without pores and strong interaction between crystals and network. The process has the potential to generate a new class of hybrid materials that would be available on the macroscopic scale for use in lightweight design and medicine.

Well-defined amphiphilic poly(2-oxazoline) ABA-triblock copolymers and their aggregation behavior in aqueous solution.

Self-organization of block copolymers in solution is a way to obtain advanced functional superstructures. The synthesis of well-defined polymethyloxazoline-block-polyphenyloxazoline-block-polymethyloxazoline triblock copolymers is described and proven by (1) H NMR spectroscopy, SEC, and ESI-MS. The surprisingly water- soluble block copolymers do self-organize in aqueous solutions uniquely forming three coexisting well-defined structures: unimolecular micelles, micellar aggregates, and very form-stable polymersomes. This is the first example of a polymersome forming ABA-triblock copolymer with a glassy middle block. The spherical vesicles are analysed by scanning electron microscopy and transmission electron microscopy. It could be shown that these vesicles are indeed hollow spheres.