Biocompatibility and Physiological Thiolytic Degradability of Radically-made Thioester-functional Copolymers

Being non-degradable, vinyl polymers have limited biomedical applicability. Unfortunately, backbone esters incorporated through conventional radical ring-opening methods do not undergo appreciable abiotic hydrolysis under physiologically relevant conditions. Here, PEG acrylate and di(ethylene glycol) acrylamide-based copolymers containing backbone thioesters were prepared through the radical ring-opening copolymerization of the thionolactone dibenzo[c,e]oxepin-5(7H)-thione. The thioesters degraded fully in the presence of 10 mM cysteine at pH 7.4, with the mechanism presumed to involve an irreversible S–N switch. Degradations with N-acetylcysteine and glutathione were reversible through the thiol–thioester exchange polycondensation of R–SC(=O)–polymer–SH fragments with full degradation relying on an increased thiolate:thioester ratio. Treatment with 10 mM glutathione at pH 7.2 (mimicking intracellular conditions) triggered an insoluble–soluble switch of a temperature-responsive copolymer at 37 °C and the release of encapsulated Nile Red (as a drug model) from core-degradable diblock copolymer micelles. Copolymers and their cysteinolytic degradation products were found to be non-cytotoxic, making thioester backbone-functional polymers promising for drug delivery applications.

3D printing of functional polymers for miniature machines

Miniature robots and actuators with micrometer or millimeter scale size can be driven by diverse power sources, e.g., chemical fuels, light, magnetic, and acoustic fields. These machines have the potential to access complex narrow spaces, execute medical tasks, perform environmental monitoring, and manipulate micro-objects. Recent advancements in 3D printing techniques have demonstrated great benefits in manufacturing small-scale structures such as customized design with programmable physical properties. Combining 3D printing methods, functional polymers, and active control strategies enables these miniature machines with diverse functionalities to broaden their potentials in medical applications. Herein, this review provides an overview of 3D printing techniques applicable for the fabrication of small-scale machines and printable functional materials, including shape-morphing materials, biomaterials, composite polymers, and self-healing polymers. Functions and applications of tiny robots and actuators fabricated by 3D printing and future perspectives toward small-scale intelligent machines are discussed.

Molecular Structuring of Novel Chiral Polymers via Cyclophane-based Monomer Design Strategies

Structuring soft matter with precise control over molecular arrangements, nanoscale morphologies, especially aiming at functional polymers featuring chirality or helicity, responsiveness, and other features, has been a great research objective, which yet remains a challenging task. In this research work, we developed new design strategies for molecular structuring of an entirely new class of chiral polymers based on [2.2]paracyclophane derivatives. The grafting of tunable functional moieties onto [2.2]paracyclophane enables post-polymerization modification, where diverse perspective applications can be envisioned. In particular, chiral vinyl[2.2]paracyclophane and [2.2]paracyclophane-substituted diazoacetate give novel poly[2.2]paracyclophanylethenes and poly[2.2]paracyclophanylmethenes, respectively.

Symmetric RAFT-agent for synthesizing multiblock copolymers with different activated monomers

With a bifunctional symmetric RAFT agent well-defined polymer structures can be achieved. This paper shows the possibility to synthesize block copolymer systems consisting out of different activated monomers. With the novel bifunctional symmetric RAFT agent water-born polymer systems with a block structure (B-b-A-b-B) can be polymerized. The symmetric RAFT agent is designed to polymerize both more activated monomers (A) and less activated monomers (B). Due to the ability of a controlled radical polymerization of different activated monomers the dispersity of the resulting polymers is broader compared to common RAFT polymerizations. In regard to industrial applications like emulsifiers, stabilizers or viscosity modifiers the broader molecular weight distribution has no impact. Overall, this paper shows the possibility towards new functional polymers with unique properties.