Small-Molecule Modulation of Soft-Matter Frank–Kasper Phases: A Method for Adding Function to Form

Incorporation of small amounts of α-tocopherol (vitamin E) in blends with the cellobiose–triazole-linked atactic poly(4-methyl-1-pentene) (CB-aPMP) sugar–polyolefin conjugate can be used to exert external control over thermotropic phase behavior and provide access to non-canonical soft matter Frank–Kasper A15 and σ phases. These results establish a paradigm that can be used for the further design and development of scalable quantities of soft matter FK phases of increased structural complexity and functional capability.     

Structural investigation of Nd-zirconolite irradiated with He+ ions

Journal of Radioanalytical and Nuclear Chemistry - Zirconolite, a potential candidate for the immobilization of actinides was investigated for the induced effects of α-particles simulated...     

Complex Study of the Spearhead Superficial Crust from Burial Mound no. 1 near Novosvobodnaya Village

A complex study of a spearhead dated back to IV mill. BC from burial mound no. 1 near Novosvobodnaya village (collection of the State Historical Museum) and, in particular, the material of spearhead superficial crust has been performed. The elemental and phase composition of the metal of spearhead and the superficial crust on its surface have been determined by scanning electron microscopy, jointly with energydispersive X-ray microanalysis and X-ray phase analysis. A comparative analysis of the results of studying the spearhead superficial crust and similar crusts on other artifacts from the mounds near Novosvobodnaya village suggest natural origin of the crust on copper?arsenic artifacts.

     

Domain-based local pair natural orbital methods within the correlation consistent composite approach

Ab initio composite approaches have been utilized to model and predict main group thermochemistry within 1 kcal mol⁻¹, on average, from well-established reliable experiments, primarily for molecules with less than 30 atoms. For molecules of increasing size and complexity, such as biomolecular complexes, composite methodologies have been limited in their application. Therefore, the domain-based local pair natural orbital (DLPNO) methods have been implemented within the correlation consistent composite approach (ccCA) framework, namely DLPNO-ccCA, to reduce the computational cost (disk space, CPU (central processing unit) time, memory) and predict energetic properties such as enthalpies of formation, noncovalent interactions, and conformation energies for organic biomolecular complexes including one of the largest molecules examined via composite strategies, within 1 kcal mol⁻¹, after calibration with 119 molecules and a set of linear alkanes. © 2019 Wiley Periodicals, Inc.     

Rational Development of Remote C−H Functionalization of Biphenyl: Experimental and Computational Studies

A simple and efficient nitrile-directed meta-C−H olefination, acetoxylation, and iodination of biaryl compounds is reported. Compared to the previous approach of installing a complex U-shaped template to achieve a molecular U-turn and assemble the large-sized cyclophane transition state for the remote C−H activation, a synthetically useful phenyl nitrile functional group could also direct remote meta-C−H activation. This reaction provides a useful method for the modification of biaryl compounds because the nitrile group can be readily converted to amines, acids, amides, or other heterocycles. Notably, the remote meta-selectivity of biphenylnitriles could not be expected from previous results with a macrocyclophane nitrile template. DFT computational studies show that a ligand-containing Pd–Ag heterodimeric transition state (TS) favors the desired remote meta-selectivity. Control experiments demonstrate the directing effect of the nitrile group and exclude the possibility of non-directed meta-C−H activation. Substituted 2-pyridone ligands were found to be key in assisting the cleavage of the meta-C−H bond in the concerted metalation–deprotonation (CMD) process.     

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.