In this paper, we investigate the influence of selected reaction parameters on the formation of surface-attached polymer monolayers. The process is based on the use of self-assembled monolayers containing a polymerizable group and the performance of a bulk free radical polymerization reaction (“grafting through polymerization”). To this, methacryl moieties were immobilized on silica gel surfaces via a silane linker. During the polymerization reaction in a conventional way, free polymer is formed in solution. However, every now and then during chain growth also surface-attached monomers become integrated in the polymer chains, leading instantaneously to covalent linking of the growing polymer molecules to the surfaces. As more and more polymer chains become attached, this leads to the formation of a surface-attached polymer layer on the silica surface. Various sets of polymerization reactions were performed and the influence of a variation of temperature, reaction time and concentration of monomer, initiator, and immobilized monomer onto the layer formation are investigated. We propose a model of the layer formation process and the grafting-through process is compared to grafting-to and grafting-from techniques.

Triple‐T trick! Traceless tosylhydrazone‐based triazole formation is readily achieved by reacting primary amines with functional α,α‐dichlorotosylhydrozones under ambient conditions. This fast and efficient alternative affords exclusively 1,4‐substituted triazole “click products” with complete retention of configuration. Primary amines, inherent to many natural products, can be modified in this way without protecting group manipulations.

Thromboembolism is a severe complication in patients with ventricular assist devices. Interactions of platelets with the artificial surface and pathological blood flow conditions could contribute to thrombus formation. Previous studies suggested that strongly swellable polymer coatings prepared from various poly(N-alkyl acrylamides) are bioinert as they repel proteins and cells. In this study, we tested structurally similar polymer coatings with varying degrees of crosslinking and swelling to explore if the bioinert character of such coatings is also valid under whole blood perfusion and shear stress. Glass substrates coated with medical grade polyurethane (PU) were modified with surface-attached poly(N-alkyl acrylamide) layers, which differed in crosslinking and in swelling. Slides were perfused with human blood containing fluoresceinated platelets at a shear rate of 1500 s for 3 minutes. Noncoated and PU-coated glass slides served as a reference for thrombogenic surfaces. We detected severe platelet adhesion on the reference surfaces. There was no platelet adhesion on poly(N-alkyl acrylamide) coatings with a swelling factor above 1.5-2 (p < 0.001 compared with PU). A lower swelling factor resulted in severe platelet adhesion. Different degrees of crosslinking ranging from 1% to 10% did not reverse platelet repellent properties of the representative polymer tested (p < 0.001 compared with PU).

Protein profiling probes are important tools for studying the composition of the proteome and as such have contributed greatly to the understanding of various complex biological processes in higher organisms. For this purpose the application of fluorescently labeled activity or affinity probes is highly desirable. Especially for in vivo detection of low abundant target proteins, otherwise difficult to analyse by standard blotting techniques, fluorescently labeled profiling probes are of high value. Here, a one-pot protocol for the synthesis of activated fluorescent labels (i.e. azide, alkynyl or NHS), based on the Ugi-4-component reaction (Ugi-4CR), is presented. As a result of the peptoidic structure formed, the fluorescent properties of the products are pH insensitive. Moreover, the applicability of these probes, as exemplified by the labeling of model protein BSA, will be discussed.

We report on the generation of surface attached polymer networks through C,H insertion reactions based on carbene intermediates. To this copolymers based on N,Ndimethyl acrylamide, which contain a-diazo ester groups, are generated and coated onto a solid substrate covered with a self-assembled monolayer of a silane. After deposition, films having thicknesses of approximately 120 nm are irradiated with UV light having a wavelength of 254 nm or 360 nm or heated to temperatures between 80 and 180 8C. During the light or heat-induced activation process, carbenes are formed, which react via CAH insertion with any neighboring polymer chain and/or with the self-assembled monolayer on the substrate, thus forming surface-attached polymer networks. To follow the kinetics of the crosslinking process, the conditions are adjusted, so that they range between 5 and 10 min for the UVcrosslinking and 5 to 15 min for the heat-induced crosslinking. UV-patterning of the surface-attached polymer networks through chrome contact masks allows generation of microstructures in the micrometer range. We investigate the layer formation process and describe the formation of microstructured surfaces based on these surface-attached polymer networks.