The redox switchable formation of very well-defined supramolecular graft polymers in aqueous solution driven by host-guest interactions between ferrocene (Fc) and cyclodextrin (CD) is presented. The Fc-containing acrylic backbone copolymer (PDMA-stat-Fc) is prepared via reversible addition-fragmentation chain transfer (RAFT) copolymerization of N,N-dimethyl-acrylamide (DMA) and the novel monomer N-(ferrocenoylmethyl)acrylamide (NFMA). Via the RAFT process, copolymers containing variable Fc ratios (5-10 mol%) are prepared, affording polymers of molecular masses of close to 11,000 g mol(-1) and molar mass dispersities (Đ) of 1.2. The β-cyclodextrin (β-CD) containing building block is synthesized via RAFT-polymerization, too, in order to afford a polymer with well-defined molecular mass and low dispersity (Mn = 10 300 g mol(-1) , Đ = 1.1), employing a propargyl-functionalized chain transfer agent for the polymerization of N,N-diethylacrylamide (DEA). The polymerization product is subsequently terminated with β-CD via the regiospecific copper (I)-catalyzed 1,3-cycloaddition (PDEA-βCD). Host-guest interactions between Fc and CD lead to the formation of supramolecular graft-polymers, verified via nuclear Overhauser enhancement spectroscopy (NOESY). Importantly, their redox-responsive character is clearly confirmed via cyclic voltammetry (CV). The self-assembly of the statistical Fc-containing lateral polymer chain in aqueous solution leads to mono- and multi-core micelle-aggregates evidenced via TEM. Only diffused cloud-like, non-spherical nanostructures are observed after addition of PDEA-βCD (TEM).

Iodonium sulfonates are proposed here as a new class of high‐performance coinitiators for camphorquinone (CQ)‐based systems for the polymerization of methacrylates under blue light irradiation. When combined with CQ, the new proposed coinitiators present excellent polymerization performances and are excellent candidates for the replacement of tertiary aromatic amines subjected to toxicological concerns in the well‐established CQ/amine photoinitiating system (PIS). Remarkably, good bleaching properties are obtained after polymerization. The use of the new PIS for dental adhesives is also investigated. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1664–1669

Due to their magneto‐mechanical coupling and biocompatibility, Fe‐Pd based ferromagnetic shape memory alloys are a highly promising materials class for application as contact‐less magneto‐mechanical transducers in biomedical environments. For use in cell and tissue actuators or strain sensors, sufficient adhesion to mediate strains clearly constitutes a prerequisite. As the RGD sequence is the most important binding motif for mammalian cells, which they express to facilitate adhesion, the potential of RGD coatings to achieve this goal is explored. Employing large‐scale density functional theory calculations the physics of bonding between RGD and Fe‐Pd surfaces, which is characterized by coordinate bonds of O and N atoms to Fe, accompanied by electrostatic contributions, is clarified. Theoretical predictions on adhesion, that are confirmed experimentally, suggest RGD as suitable strain mediator to Fe‐Pd surfaces. On the cell side, favorable adhesion properties of RGD‐coated Fe‐Pd are manifested in cell morphology and spreading behavior. Demonstrating that the adhesion forces between RGD and Fe‐Pd exceed those exerted by cells to the RGD coating, as well as traction forces acting onto integrin bonds, the findings pave the way for novel type of applications as cell and tissue actuator or sensor within the areas of tissue engineering and regenerative medicine.

The use of safe, economic, and efficient initiators in redox free radical polymerization (RFRP) at room temperature (RT) or in cationic polymerization (CP) and as photoinitiators (PI) for both free radical polymerization (FRP) and CP as well as their use for the manufacture of composites are investigated. Remarkably, initiators based on silane/iodonium salt couples are proposed here for their versatility for all the different polymerization modes which is a quite unique feature. The reactions are followed by optical pyrometric measurements, DSC (differential scanning calorimetry), RT-FTIR (real-time Fourier transformed infrared spectrometry), and CRM (confocal Raman microscopy). In RFRP, an adjustable gel time can be controlled between 1 and 15 min by adjusting the concentrations of these redox agents (or even between 2 and 30 min upon addition of stabilizer, e.g., TEMPOL); the storage stability over 5 weeks at ambient temperature and in the dark is excellent. In FRP, up to 80% of reactive function conversion is reached. In CP, the DSC peak drops down from 175 °C (in absence of silane) to 113 °C. Remarkably, carbon or glass fiber/epoxy resin composites are easily obtained through a dual approach (two steps), i.e., fast photochemical curing for the surface associated with redox or thermal curing in depth.