Visible-Light-Driven MADIX Polymerisation via a Reusable, Low-Cost, and Non-Toxic Bismuth Oxide Photocatalyst.

The continuous amalgamation of photocatalysis into existing reversible deactivation radical polymerisation (RDRP) processes has initiated a rapidly propagating area of polymer research in recent years. We introduce bismuth oxide (Bi2 O3 ) as a heterogeneous photocatalyst for polymerisations, operating at room temperature with visible light. We demonstrate formidable control over degenerative chain-transfer polymerisations, such as macromolecular design by interchange of xanthate (MADIX) and reversible addition-fragmentation chain-transfer (RAFT) polymerisation. We achieved narrow molecular weight distributions and attribute the excellent temporal control of a photo-induced electron transfer (PET) process. This methodology was employed to synthesise diblock copolymers combining differently activated monomers. The Bi2 O3 catalyst system has the additional benefits of low toxicity, reusability, low-cost, and ease of removal from the reaction mixture.

A facile route to segmented copolymers by fusing ambient temperature step-growth and RAFT polymerization.

We introduce the facile synthesis of segmented copolymers by a catalyst-free Diels-Alder (DA) reaction at ambient temperature via step-growth and subsequent reversible addition fragmentation chain transfer (RAFT) polymerization. High molecular weight step-growth polymers are readily obtained (Mw = 40 000 g mol-1), featuring trithiocarbonate moieties in their chain, which allow monomer insertion via RAFT polymerization yielding high molecular weight species.

Self-Reporting Fluorescent Step-Growth RAFT Polymers Based on Nitrile Imine-Mediated Tetrazole-ene Cycloaddition Chemistry.

We introduce an inherently fluorescent self-reporting step-growth polymer system as well as a fluorescence-based methodology for accessing the kinetics of the underpinning photoinduced nitrile imine-mediated tetrazole-ene cycloaddition (NITEC) process, using an equimolar mixture of a bismaleimide linker and a bifunctional α,ω-tetrazole-chain transfer agent (CTA). Similarly, α,ω-tetrazole-capped polystyrene, prepared via RAFT polymerization, was employed as a photoreactive macromonomer. Upon UV irradiation, the tetrazole moiety readily reacts with activated dialkenes producing the fluorescent pyrazoline-containing polymer. Thus, the fluorescence emission of the step-growth polymers is directly correlated with the number of ligation points in the polymer, forming an ideal self-reporting sensor system. The viability of the fluorescence-based quantification is verified via NMR spectroscopy, evidencing that fluorescence-based polymerization monitoring is a viable avenue in cases where NMR spectroscopy is difficult to conduct.

Spatially resolved photochemical coding of reversibly anchored cysteine-rich domains.

We present a novel methodology to generate recodable surfaces using cysteine-rich domains (CRD) via a combination of photolithography and reversible covalently peptide-driven disulfide formation. Therefore, two 21mer CRD peptide derivatives were synthesized, one bearing an electron deficient fumarate group for immobilization via nitrile imine-ene mediated cycloaddition (NITEC) to a tetrazole-functional surface. Secondly, a bromine moiety is introduced to the CRD for analytic labelling purposes to detect surface encoding. The photolithography is conducted by selectively passivating the surface with a polyethylene glycol (PEG)-fumarate via NITEC using a photomask in a dotted pattern. Consecutively, the CRD-fumarate is immobilized via NITEC adjacent to the PEG-functional areas to the unaffected tetrazole covered surface layer. Subsequently, the CRD-bromide is covalently linked to the CRD-fumarate by forming disulfide bonds under mild reoxidative conditions in a buffer solution. The CRD-bromide is released from the surface upon reduction to recover the prior state of the surface without the bromine marker. The analysis of the CRD precursors is based on electrospray ionization mass spectrometry (ESI-MS). The surface analytics were carried out via time-of-flight secondary ion mass spectrometry (ToF-SIMS), unambiguously verifying the successful immobilization as well as coding and decoding of the CRD-bromide on the surface based on dynamically reversible disulfide bond formation.

"Patchy" Carbon Nanotubes as Efficient Compatibilizers for Polymer Blends.

Surface-modified carbon nanotubes (CNTs) have become well-established filler materials for polymer nanocomposites. However, in immiscible polymer blends, the CNT-coating is selective toward the more compatible phase, which suppresses their homogeneous distribution and limits harnessing the full potential of the filler. In this study, we show that multiwalled CNTs with a patchy polystyrene/poly(methyl methacrylate) (PS/PMMA) corona disperse equally well in both phases of an incompatible PS/PMMA polymer blend. Unlike polymer-grafted CNTs with a uniform corona, the patchy CNTs are able to adjust their corona structure to the blend phases by selective swelling/collapse of respective miscible/immiscible surface patches. Importantly, the high interfacial activity of patchy CNTs further causes a significant decrease in PMMA droplet size with increasing filler content. The combined effect of compatibilization and homogeneous distribution makes patchy CNTs interesting materials for polymer blend nanocomposites, where next to the compatibilization, a homogeneous filler distribution is important to gain the desired materials property (e.g., reinforcement).

Crowdsourcing: Global search and the twisted roles of consumers and producers.

Crowdsourcing spreads and morphs quickly, shaping areas as diverse as creating, organizing, and sharing knowledge; producing digital artifacts; providing services involving tangible assets; or monitoring and evaluating. Crowdsourcing as sourcing by means of 'global search' yields four types of values for sourcing actors: creative expertise, critical items, execution capacity, and bargaining power. It accesses cheap excess capacities at the work realm's margins, channeling them toward production. Provision and utilization of excess capacities rationalize society while intimately connecting to a broader societal trend twisting consumers' and producers' roles: leading toward 'working consumers' and 'consuming producers' and shifting power toward the latter. Similarly, marketers using crowdsourcing's look and feel to camouflage traditional approaches to bringing consumers under control preserve producer power.