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In this work, we report the synthesis, photophysics, and electrochemistry of a new array of trinuclear complexes, [(bpy)2Os(d-HIm-t)M(t-HIm-d)Os(bpy)2]6+ (M = FeII, RuII, and OsII), based on a previously reported bipyridine-terpyridine type bridge (d-HIm-t). Photophysical behavior of in situ generated trinuclear OsZnOs complex [(bpy)2Os(d-HIm-t)Zn(t-HIm-d)Os(bpy)2]6+ was also investigated to understand the complicated photophysics of trinuclear array. Complexes display very rich redox properties demonstrating multiple metal-based oxidation and ligand-based reduction couples. The triads exhibit strong absorption throughout the entire UV-vis spectral region and also emit in the near-infrared domain (NIR) with a sufficiently long lifetime at ambient temperature. Intercomponent energy transfer, either from the periphery to the center or from the center to the periphery, depending upon the relative position of metals, was convincingly demonstrated through steady-state emission and lifetime measurements of the triads together with respective model complexes. Interestingly, Fe2+ does not worsen the emission behavior of the OsFeOs system to a great extent. Present trinuclear complexes act as a visible light absorbing antenna by funneling the absorbed light to the subunit(s) with the lowest energy excited state.Three n-type fused lactam semiconducting polymers were synthesized for thermoelectric and transistor applications via a cheap, highly atom-efficient, and nontoxic transition-metal free aldol polycondensation. Energy level analysis of the three polymers demonstrated that reducing the central acene core size from two anthracenes (A-A), to mixed naphthalene-anthracene (A-N), and two naphthalene cores (N-N) resulted in progressively larger electron affinities, thereby suggesting an increasingly more favorable and efficient solution doping process when employing 4-(2,3-dihydro-1,3-dimethyl-1H-benzimidazol-2-yl)-N,N-dimethylbenzenamine (N-DMBI) as the dopant. CHR2797 price Meanwhile, organic field effect transistor (OFET) mobility data showed the N-N and A-N polymers to feature the highest charge carrier mobilities, further highlighting the benefits of aryl core contraction to the electronic performance of the materials. Ultimately, the combination of these two factors resulted in N-N, A-N, and A-A to display power factors (PFs) of 3.2 μW m-1 K-2, 1.6 μW m-1 K-2, and 0.3 μW m-1 K-2, respectively, when doped with N-DMBI, whereby the PFs recorded for N-N and A-N are among the highest reported in the literature for n-type polymers. Importantly, the results reported in this study highlight that modulating the size of the central acene ring is a highly effective molecular design strategy to optimize the thermoelectric performance of conjugated polymers, thus also providing new insights into the molecular design guidelines for the next generation of high-performance n-type materials for thermoelectric applications.Plasmalogens are vinyl ether-containing lipids produced by mammals and bacteria. The aerobic biosynthetic pathway in eukaryotes and bacteria is known, but the anaerobic pathway has remained a mystery. Here, we describe a two-gene operon (plasmalogen synthase, pls) responsible for plasmalogen production in the anaerobic bacterium Clostridium perfringens. While aerobic plasmalogen biosynthesis involves an oxidative conversion of an ether to a vinyl ether, anaerobic plasmalogen biosynthesis uses the reductive conversion of an ester to an aldehyde equivalent. Heterologous expression of the C. perfringens pls operon in E. coli conferred the ability to produce plasmalogens. The pls operon is predicted to encode a multidomain complex similar to benzoyl-CoA reductase/hydroxylacyl-CoA dehydratase (BCR/HAD) enzymes. Versions of this operon can be found in a wide range of obligate and facultative anaerobic bacteria, including many human gut microbes.Lipid extracts of the fungus Flammulina velutipes were found to contain various scarce fatty acids including dodec-11-enoic acid and di- and tri-unsaturated C16 isomers. A biotechnological approach using a heterologously expressed carboxylic acid reductase was developed to transform the fatty acids into the respective aldehydes, yielding inter alia dodec-11-enal. Supplementation studies gave insights into the fungal biosynthesis of this rarely occurring acid and suggested a terminal desaturation of lauric acid being responsible for its formation. A systematic structure-odor relationship assessment of terminally unsaturated aldehydes (C7-C13) revealed odor thresholds in the range of 0.24-22 μg/L in aqueous solution and 0.039-29 ng/L in air. In both cases, non-8-enal was identified as the most potent compound. All aldehydes exhibited green odor qualities. Short-chained substances were additionally associated with grassy, melon-, and cucumber-like notes, while longer-chained homologs smelled soapy and coriander leaf-like with partly herbaceous nuances. Dodec-11-enal turned out to be of highly pleasant scent without off-notes.A gold-catalyzed N,O-acetal formation was established to construct an amide/carbamate-linked N,O-acetal substructure with bulky alcohols. The acyliminium cation species generated from o-alkynylbenzoic acid ester in the presence of a gold catalyst is highly reactive and underwent nucleophilic attack of various bulky alcohols and phenols at room temperature under neutral conditions, leading to the corresponding N,O-acetals in yields of 34-89% with good functional group tolerance.A visible-light-driven protocol for the synthesis of aryl trifluoromethyl thioethers under photocatalyst- and metal-free conditions has been pursued. The procedure exploits the peculiar properties of arylazo sulfones (having electron-rich or electron-poor substituents on the (hetero)aromatic ring) as photochemical precursors of aryl radicals and S-trifluoromethyl arylsulfonothioates as easy-to-handle trifluoromethylthiolating agents.We assess the potential for formulating a porous liquid that could be used as a selective solvent for the separation of ethane and ethene. Ethane-ethene separation is performed on very large scales by cryogenic distillation, but this uses large amounts of energy. Solvents that are selective to ethane or ethene could potentially enable more efficient liquid-based separation processes to be developed, but to date such solvents have been elusive. Here, Type 3 porous liquids, which consist of microporous solids dispersed in size-excluded liquid phases, were tailored toward the separation of ethane and ethene. A high selectivity for ethene over ethane (25.6 at 0.8 bar) and a high capacity was achieved for zeolite AgA dispersed in an Ag-containing ionic liquid. Unusually for liquid phases, the selectivity for ethane over ethene (2.55 at 0.8 bar) could also be achieved using either the metal-organic framework (MOF) Cu(Qc)2 (Qc = quinoline-5-carboxylate) dispersed in sesame oil or ZIF-7 in sesame oil, the latter showing gated uptake.