Selbstheilende Polymere

Even though the field of self‐healing is rarely known so far – self healing materials are already present at our market. Nevertheless just due to modern scientific concepts we are now able to understand the basic mechanistic steps in a more detailed way. Further progress on this field will open access to materials with a wide range of adjustable properties. Therefore, applications of such self healing materials are not limited – assuming the market‐price is competitive and the elongated lifetime delivers an appropriate advantage. Already demonstrated for concrete and clear coatings for cars, the investigations done so far have generated materials with improved properties and prolonged durability.     

Living Cationic Polymerization of Vinyl Ethers through a Photoinduced Radical Oxidation/Addition/Deactivation Sequence

A new photoinitiating system for living cationic polymerization of vinyl ethers is reported. In the current approach, visible‐light irradiation of dimanganese decacarbonyl (Mn₂(CO)₁₀) in the presence of an alkyl bromide results in the formation of carbon‐centered radicals. The photochemically generated radicals were then oxidized by diphenyliodonium ions to the corresponding cations. These cations can add vinyl ether monomers, which are then rapidly deactivated by the bromide anions to give α‐halide functional end groups. Poly(vinyl ether) chains are then grown through successive photoinduced radical oxidation/addition/deactivation (PROAD) in a controlled manner. The living nature of the system is evaluated through kinetics studies and block copolymer formation.     

Completely Recyclable Monomers and Polycarbonate: Approach to Sustainable Polymers

It is of great significance to depolymerize used or waste polymers to recover the starting monomers suitable for repolymerization reactions that reform recycled materials no different from the virgin polymer. Herein, we report a novel recyclable plastic: degradable polycarbonate synthesized by dinuclear chromium‐complex‐mediated copolymerization of CO₂ with 1‐benzyloxycarbonyl‐3,4‐epoxy pyrrolidine, a meso ‐epoxide. Notably, the novel polycarbonate with more than 99 % carbonate linkages could be recycled back into the epoxide monomer in quantitative yield under mild reaction conditions. Remarkably, the copolymerization/depolymerization processes can be achieved by the ON/OFF reversible temperature switch, and recycled several times without any change in the epoxide monomer and copolymer. These characteristics accord well with the concept of perfectly sustainable polymers.     

Mussel‐Inspired Surface‐Imprinted Sensors for Potentiometric Label‐Free Detection of Biological Species

Using sensors to quantify clinically relevant biological species has emerged as a fascinating research field due to their potential to revolutionize clinical diagnosis and therapeutic monitoring. Taking advantage of the wide utility in clinical analysis and low cost of potentiometric ion sensors, we demonstrate a method to use such ion sensors to quantify bioanalytes without chemical labels. This is achieved by combination of chronopotentiometry with a mussel‐inspired surface imprinting technique. The biomimetic sensing method is based on a blocking mechanism by which the recognition reaction between the surface imprinted polymer and a bioanalyte can block the current‐induced ion transfer of an indicator ion, thus causing a potential change. The present method offers high sensitivity and excellent selectivity for detection of biological analytes. As models, trypsin and yeast cells can be measured at levels down to 0.03 U mL⁻¹ and 50 CFU mL⁻¹, respectively.     

Mechanochemical Friedel–Crafts Alkylation—A Sustainable Pathway Towards Porous Organic Polymers

This study elucidates an innovative mechanochemical approach applying Friedel–Crafts alkylation to synthesize porous covalent triazine frameworks (CTFs). Herein, we pursue a counterintuitive approach by utilizing a rather destructive method to synthesize well‐defined materials with intrinsic porosity. Investigating a model system including carbazole as monomer and cyanuric chloride as triazine node, ball milling is shown to successfully yield porous polymers almost quantitatively. We verified the successful structure formation by an in‐depth investigation applying XPS, solid‐state NMR and FT‐IR spectroscopy. An in situ study of pressure and temperature developments inside the milling chamber in combination with two‐dimensional liquid‐state NMR spectroscopy reveals insights into the polymerization mechanism. The versatility of this mechanochemical approach is showcased by application of other monomers with different size and geometry.     

Conjugated Polymer Nanoparticles to Augment Photosynthesis of Chloroplasts

By coating chloroplasts with conjugated polymer nanoparticles (CPNs), a new bio‐optical hybrid photosynthesis system (chloroplast/CPNs) is developed. Since CPNs possess unique light harvesting ability, including the ultraviolet part that chloroplasts absorb less, chloroplast/CPN complexes can capture broader range of light to accelerate the electron transport rates in photosystem II (PS II), the critical protein complex in chloroplasts, and augment photosynthesis beyond natural chloroplasts. The degree of spectral overlay between emission of CPNs and absorption of chloroplasts is critical for the enhanced photosynthesis. This work exhibits good potential to explore new and facile nanoengineering strategy for reforming chloroplast with light‐harvesting nanomaterials to enhance solar energy conversion.     

Existence of Two‐Dimensional Physical Gels even at Zero Surface Pressure at the Air/Water Interface: Rheology of Self‐Assembled Domains of Small Molecules

Films of mesoscopic domains self‐assembled from fluorocarbon/hydrocarbon diblock copolymers (FnHm ) at the air/water interface were found to display highly elastic behavior. We determined the interfacial viscoelasticity of domain‐patterned FnHm Langmuir monolayers by applying periodic shear stresses. Remarkably, we found the formation of two‐dimensional gels even at zero surface pressure. These monolayers are predominantly elastic, which is unprecedented for surfactants, exhibiting gelation only at high surface pressures. Systematic variation of the hydrocarbon (n =8; m =14, 16, 18, 20) and fluorocarbon (n =8, 10, 12; m =16) block lengths demonstrated that subtle changes in the block length ratio significantly alter the mechanics of two‐dimensional gels across one order of magnitude. These findings open perspectives for the fabrication of two‐dimensional gels with tuneable viscoelasticity via self‐assembly of mesoscale, low‐molecular‐weight materials.     

Real‐Time Control of the Enantioselectivity of a Supramolecular Catalyst Allows Selecting the Configuration of Consecutively Formed Stereogenic Centers

The enantiomeric state of a supramolecular copper catalyst can be switched in situ in ca. five seconds. The dynamic property of the catalyst is provided by the non‐covalent nature of the helical assemblies supporting the copper centers. These assemblies are formed by mixing an achiral benzene‐1,3,5‐tricarboxamide (BTA) phosphine ligand (for copper coordination) and both enantiomers of a chiral phosphine‐free BTA co‐monomer (for chirality amplification). The enantioselectivity of the hydrosilylation reaction is fixed by the BTA enantiomer in excess, which can be altered by simple BTA addition. As a result of the complete and fast stereochemical switch, any combination of the enantiomers was obtained during the conversion of a mixture of two substrates.     

Supramolecular Interfacial Polymerization: A Controllable Method of Fabricating Supramolecular Polymeric Materials

A new method of supramolecular polymerization at the water–oil interface is developed. As a demonstration, an oil‐soluble supramonomer containing two thiol end groups linked by two ureidopyrimidinone units and a water‐soluble monomer bearing two maleimide end groups are employed. Supramolecular interfacial polymerization can be implemented by a thiol–maleimide click reaction at the water–chloroform interface to obtain supramolecular polymeric films. The glass transition temperature of such supramolecular polymers can be well‐tuned by simply changing the polymerization time and temperature. It is highly anticipated that this work will provide a facile and general approach to realize control over supramolecular polymerization by transferring the preparation of supramolecular polymers from solutions to water–oil interfaces and construct supramolecular materials with well‐defined properties.