This review explores the different synthetic methods by which dispersity and MWD shape can be tuned and discusses the different properties and applications where this variation is beneficial.

Horseradish peroxidase isoenzyme C (HRP) and Engyodontium album proteinase K (proK) were immobilized inside macro- and mesoporous silica monoliths. Stable immobilization was achieved through simple noncovalent adsorption of conjugates, which were prepared from a polycationic, water-soluble second generation dendronized polymer (denpol) and the enzymes. Conjugates prepared from three denpols with the same type of repeating unit (r.u.), but different average lengths were compared. It was shown that there is no obvious advantage of using denpols with very long chains. Excellent results were achieved with denpols having on average 750 or 1000 r.u. The enzyme-loaded monoliths were tested as flow reactors. Comparison was made with microscopy glass coverslips onto which the conjugates were immobilized and with glass micropipettes containing adsorbed conjugates. High enzyme loading was achieved using the monoliths. Monoliths containing immobilized denpol–HRP conjugates exhibited good operational stability at 25 °C (for at least several hours), and good storage stability at 4 °C (at least for weeks) was demonstrated. Such HRP-containing monoliths were applied as continuous flow reactors for the quantitative determination of hydrogen peroxide in aqueous solution between 1 μM (34 ng/mL) and 50 μM (1.7 μg/mL). Although many methods for immobilizing enzymes on silica surfaces exist, there are only a few approaches with porous silica materials for the development of flow reactors. The work presented is a promising contribution to this field of research toward bioanalytical and biosynthetic applications.

We present a comprehensive investigation of main-chain scission processes affecting peripherally charged and neutral members of a class of dendronized polymers (DPs) studied in our laboratory. In these thick, sterically highly congested macromolecules, scission occurs by exposure to solvents, in some cases at room temperature, in others requiring modest heating. Our investigations rely on gel permeation chromatography and atomic force microscopy and are supported by molecular dynamics simulations as well as by electron paramagnetic resonance spectroscopy. Strikingly, DP main-chain scission depends strongly on two factors: first the solvent, which must be highly polar to induce scission of the DPs, and second the dendritic generation g. In DPs of generations 1 ≤ g ≤ 8, scission occurs readily only for g = 5, no matter whether the polymer is charged or neutral. Much more forcing conditions are required to induce degradation in DPs of g ≠ 5. We propose solvent swelling as the cause for the main-chain scission in these individual polymer molecules, explaining in particular the strong dependence on g: g < 5 DPs resemble classical polymers and are accessible to the strongly interacting, polar solvents, whereas g > 5 DPs are essentially closed off to solvent due to their more closely colloidal character. g = 5 DPs mark the transition between these two regimes, bearing strongly sterically congested side chains which are still solvent accessible to some degree. Our results suggest that, even in the absence of structural elements which favour scission such as cross-links, solvent swelling may be a generally applicable mechanochemical trigger. This may be relevant not only for DPs, but also for other types of sterically strongly congested macromolecules.

Polymeric nano‐ and microscale materials bear significant potential in manifold applications related to biomedicine. This is owed not only to the large chemical diversity of the constituent polymers, but also to the various morphologies these materials can achieve, ranging from simple particles to intricate self‐assembled structures. Modern synthetic polymer chemistry permits the tuning of many physicochemical parameters affecting the behavior of polymeric nano‐ and microscale materials in the biological context. In this Perspective, an overview of the synthetic principles underlying the modern preparation of these materials is provided, aiming to demonstrate how advances in and ingenious implementations of polymer chemistry fuel a range of applications, both present and prospective.