Aryl Boronic Acid Catalysed Dehydrative Substitution of Benzylic Alcohols for C−O Bond Formation

A combination of pentafluorophenylboronic acid and oxalic acid catalyses the dehydrative substitution of benzylic alcohols with a second alcohol to form new C−O bonds. This method has been applied to the intermolecular substitution of benzylic alcohols to form symmetrical ethers, intramolecular cyclisations of diols to form aryl-substituted tetrahydrofuran and tetrahydropyran derivatives, and intermolecular crossed-etherification reactions between two different alcohols. Mechanistic control experiments have identified a potential catalytic intermediate formed between the aryl boronic acid and oxalic acid.     

A Switch in the Hydrophobic/Hydrophilic Gas-Adsorption Character of Prussian Blue Analogues: An Affinity Control for Smart Gas Sorption

Porous coordination polymers are molecule-based materials presenting a high degree of tunability, which offer many advantages for targeted applications over conventional inorganic materials. This work demonstrates that the hydrophilic/hydrophobic character of Prussian blue analogues having a lipophilic feature may be tuned to optimize the gas adsorption properties. The role of the coordinatively unsaturated metal sites is emphasized through a combination of theoretical and experimental study of water, ethanol, and n-hexane adsorption.     

Supramolecular Tuning Enables Selective Oxygen Reduction Catalyzed by Cobalt Porphyrins for Direct Electrosynthesis of Hydrogen Peroxide

We report a supramolecular strategy for promoting the selective reduction of O₂ for direct electrosynthesis of H₂O₂. We utilized cobalt tetraphenylporphyrin (Co-TPP), an oxygen reduction reaction (ORR) catalyst with highly variable product selectivity, as a building block to assemble the permanently porous supramolecular cage Co-PB-1(6) bearing six Co-TPP subunits connected through twenty-four imine bonds. Reduction of these imine linkers to amines yields the more flexible cage Co-rPB-1(6). Both Co-PB-1(6) and Co-rPB-1(6) cages produce 90–100 % H₂O₂ from electrochemical ORR catalysis in neutral pH water, whereas the Co-TPP monomer gives a 50 % mixture of H₂O₂ and H₂O. Bimolecular pathways have been implicated in facilitating H₂O formation, therefore, we attribute this high H₂O₂ selectivity to site isolation of the discrete molecular units in each supramolecule. The ability to control reaction selectivity in supramolecular structures beyond traditional host–guest interactions offers new opportunities for designing such architectures for a broader range of catalytic applications.     

IR and Raman spectra with Gaussian-09 molecular analysis of some other parameters and vibrational spectra of 5-fluoro-uracil

Research on Chemical Intermediates - Recorded IR and Raman spectra of 5-fluoro-uracil have been analyzed with the carried out theoretical computation by Gaussian-09 [DFT/B3LYP/6-311?++G**]...     

Triphilic pentablock copolymers with perfluoroalkyl segment in central position

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.     

Planar AIEgens with Enhanced Solid-State Luminescence and ROS Generation for Multidrug-Resistant Bacteria Treatment

Planar luminogens have encountered difficulties in overcoming intrinsic aggregation-caused emission quenching by intermolecular π-π stacking interactions. Although excited-state double-bond reorganization (ESDBR) can guide us on designing planar aggregation-induced emission (AIE) luminogens (AIEgens), its mechanism has yet been elucidated. Major challenges in the field include methods to efficiently restrict ESDBR and enhance AIE performance without using bulky substituents (e.g., tetraphenylethylene and triphenylamine). In this study, we rationally developed fluoro-substituent AIEgens with stronger intermolecular H-bonding interaction for restricted molecular motions and increased crystal density, leading to decreased nonradiative decay rate by one order of magnitude. The adjusted ESDBR properties also show a corresponding response to variation in viscosity. Furthermore, their aggregation-induced reactive oxygen species (ROS) generations have been discovered. The application of such planar AIEgen in treating multidrug-resistant bacteria has been demonstrated in a mouse model. The relationship between ROS generation and distinct E/Z-configurational stacking behaviors have been further understood, providing a design principle for synthesizing planar AIEgen-based photosensitizers.