Decomposition by microorganisms of plastics in soils is almost unexplored despite the fact that the majority of plastics released into the environment end up in soils. Here, we investigate the decomposition process and microbiome of one of the most promising biobased and biodegradable plastics, poly­(butylene succinate-co-adipate) (PBSA), under field soil conditions under both ambient and future predicted climates (for the time between 2070 and 2100). We show that the gravimetric and molar mass of PBSA is already largely reduced (28–33%) after 328 days under both climates. We provide novel information on the PBSA microbiome encompassing the three domains of life: Archaea, Bacteria, and Eukarya (fungi). We show that PBSA begins to decompose after the increase in relative abundances of aquatic fungi (Tetracladium spp.) and nitrogen-fixing bacteria. The PBSA microbiome is distinct from that of surrounding soils, suggesting that PBSA serves as a new ecological habitat. We conclude that the microbial decomposition process of PBSA in soil is more complex than previously thought by involving interkingdom relationships, especially between bacteria and fungi.

Recent developments in synthetic pathways as simple reversible-deactivation radical polymerization (RDRP) techniques and quantitative post-polymerization reactions, most notoriously ‘click’ reactions, leading to segmented copolymers, have broadened the molecular architectures accessible to polymer chemists as a matter of routine. Segments can be blocks, grafted chains, branchings, telechelic end-groups, covalently attached nanoparticles, nanodomains in networks, even sequences of random copolymers, and so on. In this review, we describe the variety of the segmented synthetic copolymers landscape from the point of view of their chemical affinity, or synonymous philicity, in bulk or with their surroundings, such as solvents, permeant gases, and solid surfaces. We focus on recent contributions, current trends, and perspectives regarding polyphilic copolymers, which have, in addition to hydrophilic and lipophilic segments, other philicities, for example, towards solvents, fluorophilic entities, ions, silicones, metals, nanoparticles, and liquid crystalline moieties.

Two different microfabrication techniques for the preparation of monolithic porous polymeric 3D microstructures were assessed. The first approach is based on a radiation assisted imprint process. Electron beam initiated free radical polymerisation of acrylates/methacrylates in a porogenic solvent within the confinements of V-shaped microgrooves in a silicon master enables the pattern transfer, thereby phase separation allows for the generation of a porous material of the replicate simultaneously. Furthermore, porous 3D microstructures in the format of arrays with different feature sizes in the range of 50 to 1000 micrometers were obtained by UV exposure of a liquid film of acrylates/methacrylates in a porogenic solvent through a photomask. In this paper we present the first results regarding the combined pattern transfer and polymerisation-phase separation process in the micrometer range. Microstructures and the dimension of pores and globules within these microstructures were analysed by scanning electron microscopy.

Adding perfluoroalkyl (PF) segments to amphiphilic copolymers yields triphilic copolymers with new application profiles. Usually, PF segments are attached as terminal blocks via Cu(I) catalyzed azide-alkyne cycloaddition (CuAAC). The purpose of the current study is to design new triphilic architectures with a PF segment in central position. The PF segment bearing bifunctional atom transfer radical polymerization (ATRP) initiator is employed for the fabrication of triphilic poly(propylene oxide)-b-poly(glycerol monomethacrylate)b-PF-b-poly(glycerol monomethacrylate)-b-poly(propylene oxide) PPO-b-PGMA-b-PF-b-PGMA-b-PPO pentablock copolymers by a combined ATRP and CuAAC reaction approach. Differential scanning calorimetry indicates the PF-initiator to undergo a solid-solid phase transition at 63 C before the final crystal melting at 95 C. This is further corroborated by polarized optical microscopy and X-ray diffraction studies. The PF-initiator could successfully polymerize solketal methacrylate (SMA) under typical ATRP conditions producing well-defined Br-PSMA-b-PF-b-PSMA-Br triblock copolymers that are then converted into PPO-b-PSMA-b-PF-b-PSMA-b-PPO pentablock copolymer via CuAAC reaction. Subsequently, acid hydrolysis of the PSMA blocks afforded water soluble well-defined triphilic pentablock copolymers PPO-b-PGMA-b-PF-b-PGMA-b-PPO with fluorophilic central segment, hydrophilic middle blocks, and lipophilic outer blocks. The triphilic block copolymers could self-assemble, depending upon the preparatory protocol, into spherical and filament-like phase-separated nanostructures as revealed by transmission electron microscopy.