Innovative amperometric biosensors for monitoring the level of wastewater pollution have been constructed on the surface of the gold planar electrodes C220AT “DropSens” by using the organic–inorganic ureasil‐based composites as host matrixes and immobilized commercial laccase from Trametes versicolor. It was found that the biosensor based on the ureasil–chalcogenide glass composite is characterized by a very high sensitivity (67,540 А M−1 m−2) that is 38.3 times higher than for pure ureasil (the sensitivity of the bioelectrode was calculated as 1762 А M−1 m−2). On the other hand, application of the ureasil–chalcogenide glass composite with incorporated silver nanoparticles (NPs) synthesized by high‐dose (1.0 × 1017 Ag+/cm2) 30 keV Ag+ ion implantation results in decreasing the biosensor sensitivity up to 2390 times (the sensitivity of the bioelectrode was 28.3 А M−1 m−2). The role of additives (chalcogenide glass and silver NPs) in the ureasil matrix on the biofunctionality of the biosensors produced is considered. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45278.

Network properties of ureasil-based polymer matrixes suitable for construction of amperometric biosensors were probed by positron annihilation lifetime spectroscopy and swelling experiments. Temperature dependences of the ortho-positronium (o-Ps) lifetimes and their relative intensities were measured in a temperature range of 15-350 K. Glass transition temperatures and expansion coefficients of microscopical free-volume for the investigated polymers were determined. Differences in network behavior for the aged samples and the effect of chalcogenide (As2S3) particles on the free volume of ureasil network were observed. Swelling experiments using ethyl alcohol showed that the structure of the aged sample network had less swelling ability for the pure ureasil as well as composite. This suggests that the one of factors influencing swelling is the change of the basic ureasil network due to ageing. It is supposed that the network properties obtained by positron annihilation lifetime spectroscopy and swelling experiments could be very helpful to understand better the bio-functionality of the constructed biosensor based on the ureasil-chalcogenide glass composite.

In this study two hybrid organic-inorganic ureasilicate monomers with different length of polymer segments were chosen for preparation of sol-gel material that includes two moieties blended on the molecular scale. The first monomer was obtained by crosslinking a double terminated polyoxyalkyleneamine with an isocyanate modified silicone ethoxide and the second oneby crosslinking between the isocyanate modified silicone ethoxide with an amino modified silicone ethoxide. Sol-gel route was applied for transformation of the liquid monomer blends in transparent materials with varying degree of rigidity. The prepared samples were characterized by small-angle X-ray scattering, Fouriertransform infrared spectroscopy, positron annihilation lifetime spectroscopy, and swelling experiments. The results demonstrate that the structure of the obtained materials could be tuned by a simple variation of molar fraction ratio between these two monomers. This makes it possible to obtain nanostructured materials with predictable properties.

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