Sculpting In-plane Fractal Porous Patterns in Two-Dimensional MOF Nanocrystals for Photoelectrocatalytic CO2 Reduction

Herein, by choosing few-nm-thin two-dimensional (2D) nanocrystals of MOF-5 containing in-planner square lattices as a modular platform, a crystal lattice-guided wet-chemical etching has been rationally accomplished. As a result, two attractive pore patterns carrying Euclidean curvatures; precisely, plus(+)-shaped and fractal-patterned pores via ⟨100⟩ and ⟨110⟩ directional etching, respectively, are regulated in contrast to habitually formed spherical-shaped random etches on MOF surface. In agreement with the theoretical calculations, a diffusion-limited etching process has been optimized to devise high-yield of size-tunable fractal-pores on the MOF surface that tenders for a compatibly high payload of catalytic Re^I-complexes using the existing large edge area once modified into a free amine-group-exposed inner pore surface. Finally, on benefiting from the long-range fractal opening in 2D MOF support structure, while loaded on an electrode surface, a facilitated cross-interface charge-transportation and well-exposure of immobilized Re^I-catalysts are anticipated, thus realizing enhanced activity and stability of the supported catalyst in photoelectrochemical CO₂-to-CO reduction.     

Iron-Catalysed [3+3] Annulation of Oxime Acetates and Enaminones towards the Synthesis of Multi-Substituted Pyridines

A direct access to unsymmetrical and symmetrical multi-substituted pyridines has been accomplished via iron-catalysed [3+3] annulation of oxime acetates with enaminones. This protocol is featured by easily available starting materials, no requirement of expensive additives and ligands, operational simplicity, and good tolerance with diverse functional groups.     

Pentacoordinated Cu(II)/Zn(II) complexes bearing macrocyclic skeleton: synthesis, spectroscopic and molecular structure optimization studies

2,6-Diacetylpyridine and 1,2-diaminoethane in the presence of copper(II) and zinc(II) chlorides containing a few drops of acetic acid were condensed into compositions [CuLH2]2.2HCl.H2O (1), [Cu2LPyz]2.2HCl.4CH3COCH3 (2) [CuZnLPyz]2.2HCl.2CH3COCH3.10H2O (3) and [ZnL'Cl]3.3HCl.3H2O (4) substantiated by elemental analyses, IR, UV-vis, 1H NMR and FAB mass spectral data. Demetallation of a Ni(II) complex (isolated as above) afforded macrocyclic skeleton LH4, whereas L' symbolizes a skeleton of the ligand containing only ethylenediamine and 2,6-diacetylpyridine. Molecular structure optimization using MM2 force field calculations for the complexes revealed distorted square pyramidal geometry around Cu(II) centers in complexes 1 and 2 and tetrahedral geometry around Cu(II) and Zn(II) centers with different degrees of distortion in complex 3 whereas three Zn(II) atoms (each in distorted square pyramidal geometry) attached via Cl bridges form a cyclic structure in complex 4. In complexes 1 and 2,Cu-Cu = 2.63-2.66 angstroms indicated the possibility of coupling between the two Cu(II) centers which has been supported by lower magnetic moment as well as ESR spectra showing half-field signal.     

Influence of substrate nature on the growth of copper oxide thin films

Cu thin films were deposited on Si(111), glass, and quartz substrates by magnetron sputtering. X‐ray diffraction, SEM, and photoemission electron microscope studies were carried out to characterize the films. An influence of the nature of substrate on the Cu₂O and CuO phases formed was observed. Copper silicide formation in case of silicon substrates aided in formation of Cu₂O rather than CuO unlike glass and quartz substrates. Formation of nanocrystallites was observed by SEM and X‐ray diffraction. Copyright © 2016 John Wiley & Sons, Ltd.     

The first simultaneous sign change for Fourier coefficients of Hecke–Maass forms

The Ramanujan Journal - Let f and g be two Hecke–Maass cusp forms of weight zero for $$SL_2({mathbb {Z}})$$ with Laplacian eigenvalues $$frac{1}{4}+u^2$$ and $$frac{1}{4}+v^2$$ ,...     

A new copper complex on graphene oxide: A heterogeneous catalyst for N-arylation and C-H activation

Graphene oxide supported Cu (II) ligand complex (GO@AP/L-Cu) has been synthesized and characterized by FT-IR, Raman, PXRD, UV–Visible, TGA, XPS, FESEM, TEM, EDAX, Elemental mapping, BET, CHNS and AAS analysis. The complex has been found to be efficient and reusable heterogeneous catalyst for the N-arylation and C-H activation reactions, both the catalytic reactions were found to be simple, cleaner and give high yields (~ 90%) of product. The catalyst can be easily filtered out from the reaction mixture and reused up to four times without significant loss of catalytic activity. The reported method is economical and novel in the sense that aqueous medium was used for both the reactions and for the stability of the catalyst. All isolated organic products were fully characterized on the basis of their physical and spectral data.     

Uniformly convergent scheme for two‐parameter singularly perturbed problems with non‐smooth data

A numerical scheme is constructed for the problems in which the diffusion and convection parameters (?₁ and ?₂ , respectively) both are small, and the convection and source terms have a jump discontinuity in the domain of consideration. Depending on the magnitude of the ratios , and two different cases have been considered separately. Through rigorous analysis, the theoretical error bounds on the singular and regular components of the solution are obtained separately, which shows that in both cases the method is convergent uniformly irrespective of the size of the parameters ?₁, ?₂ . Two test problems are included to validate the theoretical results.     

Development and Validation of a Novel Stability-Indicating LC Method for the Determination of Riluzole in Bulk Drug and Tablets

A novel stability indicating LC method was developed and validated for the quantitative determination of riluzole in bulk drugs and in pharmaceutical dosage forms in the presence of its isomers, related substances and degradation products. The drug was subjected to stress conditions of hydrolysis (acid, base and neutral), oxidation, photolysis and thermal degradation. Considerable degradation was observed under base hydrolysis and oxidation. The stress samples were assayed against a qualified reference standard and the mass balance was found close to 99.5%. The developed method was validated with respect to linearity, accuracy, precision, specificity, ruggedness and robustness.     

Synthesis of unsymmetrical benzoporphyrazines in functional ionic liquids and formation of self-aggregates of zinc(II) pyridino[3,4]tribenzoporphyrazines in solutions

Unsymmetrically substituted metal-free and metallated benzoporphyrazines including pyridino[3,4]tribenzoporphyrazinic macrocycles have been synthesized in good yields by ring expansion reactions of boron(III) subphthalocyanines with phthalonitriles in functional ammonium ionic liquids in the presence of 1,8-diazabicyclo-[5,4,0]-undec-7-ene (DBU) under different reaction conditions. The concentration dependent UV/vis, fluorescence, NMR and ESI-MS spectroscopic data indicate that zinc(II) pyridino[3,4]tribenzoporphyrazines exist as head-to-tail self-aggregates in the solution phase.     

Vertically aligned and interconnected nickel oxide nanowalls fabricated by hydrothermal route

Vertically aligned and well interconnected NiO nanowalls with thin nanodiscs of cubic NiO as the in situ formed building blocks were fabricated via a template‐free approach. The alkaline solution of ammonium hydroxide was used as a reductant and Ni foil as both source material and substrate for the nanowall synthesis. Surface morphology analysis confirmed the formation of 15 nm thick and 0.2–1.5 μm wide nanowalls. The nanowalls had the crystal structure of cubic NiO with their growth plane along the [111] direction. An optical band gap of about 3.8 eV for the NiO nanowalls was obtained from the optical absorption measurement. NiO nanowalls exhibited a broad UV emission band centered at around 390 nm. This simple, but efficient synthesis technique can facilitate the growth of well aligned 2D nanostructures with large surface area for possible applications in nanoscale devices. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)