Reverse Engineering of Conjugated Microporous Polymers: Defect Structures of Tetrakis(4‐ethynylphenyl)stannane Networks

Two different conjugated microporous polymers (CMPs) based on tetrakis(4‐ethynylphenyl)stannane as the repeating unit were synthesized and their BET surfaces and thermal properties were investigated. The first direct method to elucidate the molecular structure of the organic linkers between the tin centers by digestion of the CMP is described. Selective cleavage of the tin–carbon bonds with chloroacetic acid afforded the isolated bridging units and provided insight into the surprisingly varied chemical composition of these networks.     

A Filled‐Honeycomb‐Structured Crystal Formed by Self‐Assembly of a Janus Polyoxometalate–Silsesquioxane (POM–POSS) Co‐Cluster

Clusters with diverse structures and functions have been used to create novel cluster‐assembled materials (CAMs). Understanding their self‐assembly process is a prerequisite to optimize their structure and function. Herein, two kinds of unlike organo‐functionalized inorganic clusters are covalently linked by a short organic tether to form a dumbbell‐shaped Janus co‐cluster. In a mixed solvent of acetonitrile and water, it self‐assembles into a crystal with a honeycomb superstructure constructed by hexagonal close‐packed cylinders of the smaller cluster and an orderly arranged framework of the larger cluster. Reconstruction of these structural features via coarse‐grained molecular simulations demonstrates that the cluster crystallization and the nanoscale phase separation between the two incompatible clusters synergistically result in the unique nano‐architecture. Overall, this work opens up new opportunities for generating novel CAMs for advanced future applications.     

Selective Template Removal by Thermal Depolymerization to Obtain Mesostructured Molybdenum Oxycarbide

The carbon content of mesostructured organic‐inorganic hybrid material of a cylindrical block copolymer template of poly(2‐vinylpyridine)‐block‐poly(allyl methacrylate) (P2VP‐b‐PAMA) and ammonium paramolybdate (APM) could be reduced by thermal depolymerization. By calcination in vacuo at 320 °C the PAMA core can be completely removed while the remaining P2VP brush preserves the mesostructure. The P2VP‐APM composite can then be carburized in‐situ to MoO_xC_y in a second pyrolysis step without any additional carbon source but P2VP. The molybdenum oxycarbide nanotubes obtained, form hierarchically porous non‐woven structures, which were tested as catalyst in the decomposition of NH₃. They proved to be catalytically active at temperatures above 450 °C. The activation energy was estimated from an Arrhenius Plot to be 127 kJ · mol^–1.     

Flavin Adenine Dinucleotide and N5,N10‐Methenyltetrahydrofolate are the in planta Cofactors of Arabidopsis thaliana Cryptochrome 3

Members of the cryptochrome/photolyase family (CPF) of proteins utilize noncovalently bound light‐absorbing cofactors for their biological function. Usually, the identity of these cofactors is determined after expression in heterologous systems leaving the question unanswered whether these cofactors are identical to the indigenous ones. Here, cryptochrome 3 from Arabidopsis thaliana was expressed as a fusion with the green fluorescent protein in Arabidopsis plants. Besides the confirmation of the earlier report of its localization in chloroplasts, our data indicate that fractions of the fusion protein are present in the stroma and associated with thylakoids, respectively. Furthermore, it is shown that the fusion protein expressed in planta contains the same cofactors as the His₆‐tagged protein expressed in Escherichia coli, that is, flavin adenine dinucleotide and N⁵,N¹⁰‐methenyltetrahydrofolate. This demonstrates that the heterologously expressed cryptochrome 3, characterized in a number of previous studies, is a valid surrogate of the corresponding protein expressed in plants. To our knowledge, this is also a first conclusive analysis of cofactors bound to an Arabidopsis protein belonging to the CPF and purified from plant tissue.     

Dielectric relaxation of water molecules in different lyotropic structures of nonylphenoxypoly(ethylenoxy)ethanol (Ark. 9)

Abstract

Dielectric relaxation of water molecules in the lamellar, L_α, cubic and hexagonal, H_α, lyotropic structures of nonylphenoxy-poly(ethylenoxy)ethanol (Ark. 9) has been studied by dielectric time domain spectroscopy in the frequency range between 10 MHz and 10 GHz. The values of the relaxation times, obtained at room temperature, are the following: 41 ps for the L_α phase, 29 ps for the cubic phase and 22 ps for the H_α phase. As is seen, the relaxation time of bound water is distinctly higher than that of pure water, and it depends strongly on the phase structure. The relaxation times measured for the liquid-crystalline phases as well as for pure Ark. 9 obey the Arrhenius law, and the energy barriers obtained have the following values: (20 ± 2) kJ/mol for all the liquid-crystalline phases, and (30 ± 3) kJ/mol for pure Ark. 9. The former is in good agreement with the value found for bound water in lipid systems whereas the latter is characteristic of the isotropic phase of thermotropic liquid crystals.     

Sustainable Drying and Torrefaction Processes of Miscanthus for Use as a Pelletized Solid Biofuel and Biocarbon-Carrier for Fertilizers

Miscanthus is resistant to dry, frosty winters in Poland and most European Union countries. Miscanthus gives higher yields compared to native species. Farmers can produce Miscanthus pellets after drying it for their own heating purposes. From the third year, the most efficient plant development begins, resulting in a yield of 25–30 tons of dry matter from an area of 1 hectare. Laboratory scale tests were carried out on the processes of drying, compacting, and torrefaction of this biomass type. The analysis of the drying process was conducted at three temperature levels of the drying agent (60, 100, and 140 °C). Compaction on a hydraulic press was carried out in the pressure range characteristic of a pressure agglomeration (130.8–457.8 MPa) at different moisture contents of the raw material (0.5% and 10%). The main interest in this part was to assess the influence of drying temperature, moisture content, and compaction pressure on the specific densities (DE) and the mechanical durability of the pellets (DU). In the next step, laboratory analyses of the torrefaction process were carried out, initially using the Thermogravimetric Analysis TGA and Differential Scaning Calorimeter DSC techniques (to assess activation energy (EA)), followed by a flow reactor operating at five temperature levels (225, 250, 275, 300, and 525 °C). A SEM analysis of Miscanthus after torrefaction processes at three different temperatures was performed. Both the parameters of biochar (proximate and ultimate analysis) and the quality of the torgas (volatile organic content (VOC)) were analyzed. The results show that both drying temperature and moisture level will affect the quality of the pellets. Analysis of the torrefaction process shows clearly that the optimum process temperature would be around 300–340 °C from a mass loss ratio and economical perspective.