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.

Shape memory polymers (SMPs) are an important class of smart materials. Usually, these polymers can be switched between two shapes. Recently, the possibility of switching more than two shapes was introduced for SMPs with relatively low strain storage capability. In this work, a lightly cross-linked polyethylene blend comprising 80 wt% EOC, 15 wt% LDPE, and 5 wt% HDPE is prepared in order to obtain a tunable multiple-shape memory polymer with high strain storage capacity. It is found that depending on the programming procedure, this SMP obtains a dual-, triple-, or quadruple-shape memory effect, with well-defi ned intermediate temporary shapes (retraction < 0.5% K −1 ) over a signifi cantly broad temperature range (up to 30 K), large storable strains (up to 1700%), and nearly full recovery of all shapes ( > 98.9%). transition range. [14][15][16][17][18] For instance, Xie [ 19 ] obtained a tunable multiple-shape memory for PFSA (perfl uorosulfonic acid ionomer), which possesses a broad glass transition from 55 to 130 ° C, by correlating certain temporary shapes to different temperatures within its glass transition range. Kolesov and Radusch [ 20 ] showed a triple-shape memory for cross-linked polyethylene blends of HDPE and two different ethylene-1-octene copolymers (EOC), by correlating different temporary shapes to distinct temperatures within a broad melting range. With this system, they were able to store strains of up to 100% with an intermediate shape at 44%. In general, multiple-shape memory polymers store strains of up to 240%, which limit the relative retraction response. We have recently found that the stored strain of PE-SMPs can be greatly enhanced by lowering the degree of cross-linking in a way that the resulting network is at the borderline between thermoplastics and elastomers. [ 21 ] In the present manuscript, this concept is extended to polyethylene blends in order to obtain a tunable multiple-shape memory polymer with large strain storage capability. Experimental Section MaterialsHigh density polyethylene (HDPE) (Lupolen 6021D, M w = 220 000 g mol −1 , PDI = 10, 0.5 branches per 1000 C atoms) [ 22 ]

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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.

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