Atomic-Scale Imaging of Polymers and Precision Molecular Weight Analysis.

Polymer design requires fine control over syntheses and a thorough understanding of their macromolecular structure. Herein, near-atomic level imaging of polymers is achieved, enabling the precise determination of one of the most important macromolecular characteristics: molecular weight. By judiciously designing and synthesizing different linear metal(loid)-rich homopolymers, subnanoscale polymer imaging is achieved through annular dark field-scanning transmission electron microscopy (ADF-STEM), owing to the incorporation of high atoms in the side chain of the monomeric units.

Visible light photoflow synthesis of a Cu(ii) single-chain polymer nanoparticle catalyst.

We herein pioneer the visible light ( = 410 nm) mediated flow synthesis of catalytically active single-chain nanoparticles (SCNPs). Our design approach is based on a copolymer of poly(ethylene glycol) methyl ether methacrylate and a photocleavable 2-((((2-nitrobenzyl)oxy)carbonyl)amino)ethyl methacrylate monomer which can liberate amine groups upon visible light irradiation, allowing for single-chain collapse the complexation of Cu(ii) ions. We initially demonstrate the successful applicability of our design approach for the batch photochemical synthesis of Cu(ii) SCNPs and transfer the concept to photoflow conditions, enabling, for the first time, the continuous production of functional SCNPs.

Access to Main-Chain Photoswitching Polymers via Hydroxyl-yne Click Polymerization.

Main-chain stimuli-responsive polymers synthesized via polymerization techniques that do not rely on metal-based catalysis are highly desirable for economic reasons and to avoid metal-polymer interactions. Herein, we introduce a metal-free head-to-tail organobase-catalyzed hydroxyl-yne click polymerization of an AB-type monomer to realize photoswitchable polymers featuring α-bismines as main-chain repeating units. The prepared main-chain α-bisimine-based polymers show excellent photoswitching in solution.

Photo-induced synthesis of polymeric nanoparticles and chemiluminescent degradable materials flow chemistry.

We report the photo-induced, additive-free, continuous synthesis of polymeric particles using flow chemistry. Not only can these particles be formed under ambient conditions in a solely light-induced precipitation polymerisation, they can be prepared continuous flow techniques to up-scale the synthetic process. We carefully assess the flow chemical parameters and analyse the resulting particles quantitatively using scanning electron microscopy (SEM).

Photo- and halochromism of spiropyran-based main-chain polymers.

Advanced functional polymeric materials based on spiropyrans (SPs) feature multi-stimuli responsive characteristics, such as a change in color with exposure to light (photochromism) or acids (halochromism). The inclusion of stimuli-responsive molecules in general - and SPs in particular - as main-chain repeating units is a scarcely explored macromolecular architecture compared to side chain responsive polymers. Herein, we establish the effects of substitution patterns on SPs within a homopolymer main-chain synthesized head-to-tail Acyclic Diene METathesis (ADMET) polymerization.

Molecular Photoswitching of Main-Chain α-Bisimines in Solid-State Polymers.

Photoisomerization of chromophores usually shows significantly less efficiency in solid polymers than in solution as strong intermolecular interactions lock their conformation. Herein, we establish the impact of macromolecular architecture on the isomerization efficiency of main-chain-incorporated chromophores (i.e.

Direct Visualization of Homogeneous Chemical Distribution in Functional Polyradical Microspheres.

It is demonstrated that the postfunctionalization of solid polymeric microspheres can generate fully and throughout functionalized materials, contrary to the expectation that core-shell structures are generated. The full functionalization is illustrated on the example of photochemically generated microspheres, which are subsequently transformed into polyradical systems. Given the all-organic nature of the functionalized microspheres, characterization methods with high analytical sensitivity and spatial resolution are pioneered by directly visualizing the inner chemical distribution of the postfunctionalized microspheres based on characteristic electron energy loss signals in transmission electron microscopy (TEM).

Stabilizing γ-MgH at Nanotwins in Mechanically Constrained Nanoparticles.

Reversible hydrogen uptake and the metal/dielectric transition make the Mg/MgH system a prime candidate for solid-state hydrogen storage and dynamic plasmonics. However, high dehydrogenation temperatures and slow dehydrogenation hamper broad applicability. One promising strategy to improve dehydrogenation is the formation of metastable γ-MgH .