Alkaline oxygen evolution: exploring synergy between fcc and hcp cobalt nanoparticles entrapped in N-doped graphene

Herein, we report a Mott-Schottky catalyst by entrapping cobalt nanoparticles inside the N-doped graphene shell (Co@NC). The Co@NC delivered excellent oxygen evolution activity with an overpotential of merely 248 mV at a current density of 10 mA cm^–2 with promising long-term stability. The importance of Co encapsulated in NC has further been demonstrated by synthesizing Co nanoparticles without NC shell. The synergy between the hexagonal close-packed (hcp) and face-centered cubic (fcc) Co plays a major role to improve the OER activity, whereas the NC shell optimizes the electronic structure, improves the electron conductivity, and offers a large number of active sites in Co@NC. The density functional theory calculations have revealed that the hcp Co has a dominant role in the surface reaction of electrocatalytic oxygen evolution, whereas the fcc phase induces the built-in electric field at the interfaces with N-doped graphene to accelerate the H⁺ ion transport.     

Naphthyl-(2-pyridylmethylene)amine complexes of silver(I) and ruthenium(II): synthesis,spectral studies and electrochemical behaviour

Pyridine-2-carboxaldehyde reacts with /-naphthylamine to give /-naphthyl-(2-pyridylmethylene)amine [-L (1), -L (2)]. L belongs to the unsymmetric diimine (—N=C—C=N—) family which can form five–membered chelate rings with metal ions. {donor centers are abbreviated as N[N(Py)] and N [N(nap)]} [Ag(L)₂]⁺ complexes were prepared and characterized by spectroscopic data. The reaction between L and RuCl₃ in boiling EtOH yielded green and blue–green compounds of composition RuCl₂(L)₂. I.r., u.v.–vis. and ¹H-n.m.r. data determined the stereochemistry of the complexes as trans-cis-cis (green) and cis-trans-cis (blue–green) according to the sequence of the coordination pair of Cl, N [N(Py)] and N [N(nap)]. Upon treatment of Ag(L)₂ ⁺ with Ru(bpy)₂Cl₂ in alcoholic suspension the ternary complexes, [Ru(bpy)₂(L)](ClO₄)₂, were isolated and characterized by spectroscopic data. [Ru(bpy)(L)₂](ClO₄)₂ complexes were synthesized similarly from ctc-Ru(L)₂Cl₂ and 2,2-bipyridine (bpy) in the presence of AgNO₃ and NaClO₄. These complexes show well-defined m.l.c.t transitions in the visible region. The sterochemistry of the complexes was established by ¹H-n.m.r. data. Cyclic voltammetry shows a high potential Ru^III/Ru^II couple and follows the order: [Ru(bpy)(L)₂]²⁺ > [Ru(bpy)₂(L)]²⁺ > Ru(-L)₂Cl₂ > Ru(-L)₂Cl₂.     

Aromatic-aromatic interactions in crystal structures of helical peptide scaffolds containing projecting phenylalanine residues

Aromatic-aromatic interactions between phenylalanine side chains in peptides have been probed by the structure determination in crystals of three peptides: Boc-Val-Ala-Phe-Aib-Val-Ala-Phe-Aib-OMe, I; Boc-Val-Ala-Phe-Aib-Val-Ala-Phe-Aib-Val-Ala-Phe-Aib-OMe, II; Boc-Aib-Ala-Phe-Aib-Phe-Ala-Val-Aib-OMe, III. X-ray diffraction studies reveal that all three peptides adopt helical conformations in the solid state with the Phe side chains projecting outward. Interhelix association in the crystals is promoted by Phe-Phe interactions. A total of 15 unique aromatic pairs have been characterized in the three independent crystal structures. In peptides I and II, the aromatic side chains lie on the same face of the helix at i/i + 4 positions resulting in both intrahelix and interhelix aromatic interactions. In peptide III, the Phe side chains are placed on the opposite faces of the helix, resulting in exclusive intermolecular aromatic interactions. The distances between the centroids of aromatic pair ranges from 5.11 to 6.86 A, while the distance of closest approach of ring carbon atoms ranges from 3.27 to 4.59 A. Examples of T-shaped and parallel-displaced arrangements of aromatic pairs are observed, in addition to several examples of inclined arrangements. The results support the view that the interaction potential for a pair of aromatic rings is relatively broad and rugged with several minima of similar energies, separated by small activation barriers.     

Synthesis and characterization of cobalt(II), nickel(II), copper(II), palladium(II) and dioxouranium(VI) complexes of the antipyrine Schiff base of 3-formylsalicylic acid

A new Schiff base has been synthesized from 4-aminoantipyrine and 3-formylsalicylic acid. The ligand has a dianionic tetradentate compartmental OONO donor system. The cobalt(II), nickel(II), copper(II) and dioxouranium(VI) complexes exist in phenolato-bridged dinuclear species, while palladium(II) gives a mononuclear complex with free –COOH groups. The complexes have been characterized by elemental analyses, i.r., u.v.-vis, thermal and magnetic measurements.     

Chemistry of azoimidazoles. Synthesis,spectral characterization and redox studies of N(1)-benzyl-2-(arylazo)imidazolepalladium(II)chloride

Arylazoimidazoles (2) are N,N-chelating ligands. The polymerization trend of the azolate system is restricted via N(1)-benzylation. The parent molecules (2), N(1)-benzylated products (3) and palladium complexes (4) were made by standard methods. The ligands (3) and complexes (4) are new. They have been characterized by elemental analysis, i.r., u.v.-vis. and high resolution 1H-n.m.r. spectral data. Redox studies were carried out by cyclic voltammetry. On complexation, azo reduction is shifted anodically.     

Designed helical peptides inhibit an intramembrane protease

gamma-Secretase cleaves the transmembrane domain of the amyloid precursor protein, a process implicated in the pathogenesis of Alzheimer's disease, and this enzyme is a founding member of an emerging class of intramembrane proteases. Modeling and mutagenesis suggest a helical conformation for the substrate transmembrane domain upon initial interaction with the protease. Moreover, biochemical evidence supports the presence of an initial docking site for substrate on gamma-secretase that is distinct from the active site, a property predicted to be generally true of intramembrane proteases. Here we show that short peptides designed to adopt a helical conformation in solution are inhibitors of gamma-secretase in both cells and enzyme preparations. Helical peptides with all d-amino acids are the most potent inhibitors and represent potential therapeutic leads. Subtle modifications that disrupt helicity also substantially reduce potency, suggesting that this conformation is critical for effective inhibition. Fluorescence lifetime imaging in intact cells demonstrates that helical peptides disrupt binding between substrate and protease, whereas an active site-directed inhibitor does not. These findings are consistent with helical peptides interacting with the initial substrate docking site of gamma-secretase, suggesting a general strategy for the development of potent and specific inhibitors of intramembrane proteases.     

The reactivity of the cis-RuCl2 fragment in Ru(P)2(TaiMe)Cl2 with N,O; O,O and S,S-chelators (P = PPh3; TaiMe = 1-methyl-2-(p-tolylazo)imidazole)

Ru(P)₂(TaiMe)Cl₂ [P = PPh₃; TaiMe = 1-methyl-2-(p-tolylazo)imidazole] possesses a cis-RuCl₂ configuration. Dechlorination was carried out in acetone solution by Ag⁺ and the solvated species reacted with N,O-[oxinate (ox), -picolinate (pic)], O,O-[salicylate (sa), 3-formylsalicylate (3-fsa), 5-formylsalicylate (5-fsa)] and S,S-[xanthate (xan), dithiocarbamate (dtc)] chelators to yield [Ru(P)₂(TaiMe)(N,O/O,O/S,S)] (ClO₄) _n (n = 1 for N,O- and S,S-chelators; n = 0 for O,O-chelators). The complexes were characterised by microanalysis, molar conductance, i.r., u.v.–vis. and ¹H-n.m.r. data. Isomeric structures in some complexes were identified by ¹H-n.m.r. spectra. The electronic spectra show a high intensity ( 10⁴) m.l.c.t. transition in the visible region together with a weak shoulder ( 10³) at longer wavelength. Redox studies exhibit a Ru^III/Ru^II couple and quasireversible azo reduction.     

Coumarinyl azoimidazolyl complexes of osmium(II) hydridocarbonyls: spectroscopic and structural characterization,oxidation catalysis,photovoltaic effect and density functional theory computation

Os(II) hydridocarbonyl complexes of coumarinyl azoimidazoles, [Osh(CO)(PPh₃)₂(CZ‐4R‐R′)]^0/+ ( 3 , 4 ) (CZ‐R‐H = 2‐(coumarinyl‐6‐azo)‐4‐substituted imidazole or 1‐alkyl‐2‐(coumarinyl‐6‐azo)‐4‐substituted imidazole), were characterized from spectroscopic data and the single‐crystal X‐ray data for one of the complexes, [Osh(CO)(PPh₃)₂(CZ‐4‐Ph)] ( 3c ) (CZ‐4‐Ph = 2‐(coumarinyl‐6‐azo)‐4‐phenylimidazolate), confirmed the structure. The complexes show higher emission (quantum yield ? = 0.0163–0.16) and longer lifetime (τ = 1.4–10.3 ns) than free ligands (? = 0.0012–0.0185 and τ = 0.685–1.306 ns). Cyclic voltammetry shows quasi‐reversible metal oxidation at 0.67–0.94 V for [Os(III)/Os(II)] and 1.21–1.36 V for [Os(IV)/Os(III)] and subsequent azo reductions (?0.68 to ?0.95 V for [? N?N? ]/[? N N? ]^? and irreversible < ?1.2 V for [? N N? ]^?/[? N? N? ]^2?) of the chelated coumarinyl azoimidazole. The complexes are photostable and show better photovoltaic power conversion efficiency than free ligands. Also, the complexes were used as catalysts for the oxidation of primary/secondary alcohols to aldehydes/ketones using oxidizing agents like N‐methylmorpholine N‐oxide, t‐BuOOH and H₂O₂. Density functional theory computation was carried out from the optimized structures and the data obtained were used to interpret the electronic and photovoltaic properties. Copyright © 2016 John Wiley & Sons, Ltd.     

Advances in the Bestmann–Ohira Reagent–Assisted Regioselective Synthesis of Substituted Pyrazoles,Triazoles, and Oxazoles

The Bestmann–Ohira reagent serves as a versatile platform for the regioselective construction of pyrazoles, triazoles, and oxazoles via a cycloaddition reaction and multicomponent reaction. In this review, we have summarized the most significant advances in the Bestmann–Ohira reagent (BOR)–assisted construction of functionalized five–membered heterocycles reported in the literature up to 2012.     

A Low‐Temperature Molecular Precursor Approach to Copper‐Based Nano‐Sized Digenite Mineral for Efficient Electrocatalytic Oxygen Evolution Reaction

In the urge of designing noble metal‐free and sustainable electrocatalysts for oxygen evolution reaction (OER), herein, a mineral Digenite Cu₉S₅ has been prepared from a molecular copper(I) precursor, [{(PyHS)₂Cu^I(PyHS)}₂](OTf)₂ ( 1 ), and utilized as an anode material in electrocatalytic OER for the first time. A hot injection of 1 yielded a pure phase and highly crystalline Cu₉S₅, which was then electrophoretically deposited (EPD) on a highly conducting nickel foam (NF) substrate. When assessed as an electrode for OER, the Cu₉S₅/NF displayed an overpotential of merely 298±3 mV at a current density of 10 mA cm^?2 in alkaline media. The overpotential recorded here supersedes the value obtained for the best reported Cu‐based as well as the benchmark precious‐metal‐based RuO₂ and IrO₂ electrocatalysts. In addition, the choronoamperometric OER indicated the superior stability of Cu₉S₅/NF, rendering its suitability as the sustainable anode material for practical feasibility. The excellent catalytic activity of Cu₉S₅ can be attributed to the formation of a crystalline CuO overlayer on the conductive Cu₉S₅ that behaves as active species to facilitate OER. This study delivers a distinct molecular precursor approach to produce highly active copper‐based catalysts that could be used as an efficient and durable OER electro(pre)catalysts relying on non‐precious metals.