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AbstractThis article summarizes possible applications of olefin metathesis in rubber chemistry and technology. There are three main research directives with valuable contributions to the synthesis, recycling, and characterization of elastomers. First, ring opening metathesis polymerization as well as acyclic diene metathesis polycondensation yields polyalkenamers with cross-linkable double bonds, and thus can be used for the synthesis of defined rubbers serving as raw materials in rubber technology. Secondly, by cross metathesis reaction, natural rubber (and synthetic rubber) can be functionalized resulting in telechelic polymers or small molecule specialty chemicals. Thirdly, olefin metathesis offers the possibility of degrading the cross-linked rubber network into smaller soluble pieces, enabling different analytical possibilities such as characterization of cross-linking sites, determination of rubber, rubber additives and carbon black, and exploration of the rubber–metal adhesive interface. Additionally, this route can also be used for recycling of rubber products.Graphical abstract

Herein, we report the synthesis of a novel, tetrazine-based conjugated polymer. Tetrazines have the benefit of being strong electron acceptors, while little steric hindrance is imposed on the flanking thiophene rings. Conversion of a suitably substituted nitrile precursor led to 3,6-bis(5-bromo-4-(2-octyldodecyl)thiophen-2-yl)-1,2,4,5-tetrazine (2OD-TTz). Palladium-catalyzed copolymerization of 2OD-TTz with a bithiophene monomer yielded an alternating tetrazine–quaterthiophene copolymer (PTz4T-2OD). The polymer PTz4T-2OD showed an optical band gap of 1.8 eV, a deep HOMO energy level of − 5.58 eV and good solubility. In combination with the non-fullerene acceptor ITIC-F, solar cells with power conversion efficiencies of up to 2.6% were obtained.

For the design and manufacture of complex integrated circuits, control over the threshold voltage of the transistors is essential. In the present contribution, we present a non-invasive method to tune the threshold voltage of organic thin-film transistors after device assembly over a wide range without any significant degradation of the device characteristics. This is realized by incorporating a thin, chemically reactive siloxane layer bonded to the gate oxide. This results in threshold voltages of around 70 V in the as-prepared devices. By exposing a transistor modified in this way to ammonia at different concentrations, the threshold voltage can be tuned in steps of only a few volts. This treatment affects only the charge density at the semiconductor–dielectric interface, leaving the overall shape of the transistor characteristics and the charge-carrier mobility largely unaltered.

AbstractNew alternating fluorene–thiophene copolymers are introduced bearing polar ethylene glycol-carboxylate functionalities on the thiophene ring to achieve enhanced solubility in polar solvents. Suzuki polycondensation was applied to synthesize a set of three polymers with differing lengths of the ethylene glycol side-chains. The polymers are thermally stable up to temperatures of 300 °C. Solutions of the polymers in CHCl3 show an absorption maximum at approximately 397 nm and a luminescence maximum of 472 nm in solutions with quantum yield of 30%. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels have been determined to be at −5.7 and −2.6 eV, respectively.Graphical abstract

Nickel sulfide thin films and nanocrystals stabilized with oleylamine ligands are prepared from two different nickel xanthates as single-source precursors, which decompose at approx. 180 °C, and are thereby converted into nickel sulfide. These nickel xanthates comprise branched alkyl moieties allowing the choice of a wide range of nonpolar organic solvents for the processing to nickel sulfide thin films as well as to nanoparticles. The crystal structures of both compounds show a typical square-planar coordination of the sulfur atoms of both xanthates to the nickel central atom. The thermal decomposition via the Chugaev reaction forming nickel sulfide was studied by thermal gravimetric analysis showing the reaction taking place at about 180 °C. Consequently, by thermally converting spin-coated metal xanthate films directly on the substrates in the solid state, thin films consisting of hexagonal nickel sulfide are formed. If the nickel xanthates are heated in an oleylamine solution, oleylamine-capped nickel sulfide nanocrystals are obtained, exhibiting hexagonal NiS as main phase and Ni 3 S 4 as secondary phase. This is also reflected in a sulfur-rich composition of the synthesized nickel sulfide nanocrystals as observed from TEM–EDX analyses.

AbstractMetal halide perovskites have revolutionized the field of solution-processable photovoltaics. Within just a few years, the power conversion efficiencies of perovskite-based solar cells have been improved significantly to over 20%, which makes them now already comparably efficient to silicon-based photovoltaics. This breakthrough in solution-based photovoltaics, however, has the drawback that these high efficiencies can only be obtained with lead-based perovskites and this will arguably be a substantial hurdle for various applications of perovskite-based photovoltaics and their acceptance in society, even though the amounts of lead in the solar cells are low. This fact opened up a new research field on lead-free metal halide perovskites, which is currently remarkably vivid. We took this as incentive to review this emerging research field and discuss possible alternative elements to replace lead in metal halide perovskites and the properties of the corresponding perovskite materials based on recent theoretical and experimental studies. Up to now, tin-based perovskites turned out to be most promising in terms of power conversion efficiency; however, also the toxicity of these tin-based perovskites is argued. In the focus of the research community are other elements as well including germanium, copper, antimony, or bismuth, and the corresponding perovskite compounds are already showing promising properties.Graphical abstract

Quinoxaline has recently gained interest as monomer in conjugated copolymers because of its easy synthetic accessibility and successful use in highly efficient organic solar cells. In this contribution, we introduce a quinoxaline–fluorene-co-polymer, PFQ10, synthesized by copolymerization of 5,8-dibromo-6,7-difluoro-2-[(2-hexyldecyl)oxy]quinoxaline and 9,9-dioctyl-9 H -9-fluorene-2,7-bis(boronic acid pinacol ester) using the Suzuki–Miyaura reaction. By optimization of the reaction conditions, polymers with molecular weights up to 17.2 kDa and a low dispersity of 1.3 were obtained. PFQ10 showed blue photoluminescence with an emission maximum at 459 nm and a relative fluorescence quantum yield of 0.37. As proof of principle, PFQ10 was employed in organic light-emitting diodes and showed a blue–green electroluminescence. Graphical abstract

Biobased and biodegradable polymers (BBDs) such as poly(3-hydroxy-butyrate), PHB, and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) are considered attractive alternatives to fossil-based plastic materials since they are more environmentally friendly. One major problem with these compounds is their high crystallinity and brittleness. In order to generate softer materials without using fossil-based plasticizers, the suitability of natural rubber (NR) as an impact modifier was investigated in PHBV blends. Mixtures with varying proportions of NR and PHBV were generated, and samples were prepared by mechanical mixing (roll mixer and/or internal mixer) and cured by radical C–C crosslinking. The obtained specimens were investigated with respect to their chemical and physical characteristics, applying a variety of different methods such as size exclusion chromatography, Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermal analysis, XRD, and mechanical testing. Our results clearly indicate that NR–PHBV blends exhibit excellent material characteristics including high elasticity and durability. Additionally, biodegradability was tested by applying heterologously produced and purified depolymerases. pH shift assays and morphology analyses of the surface of depolymerase-treated NR–PHBV through electron scanning microscopy confirmed the enzymatic degradation of PHBV. Altogether, we prove that NR is highly suitable to substitute fossil-based plasticizers; NR–PHBV blends are biodegradable and, hence, should be considered as interesting materials for a great number of applications.