Nano-size amorphous calcium-manganese oxide as an efficient and biomimetic water oxidizing catalyst for artificial photosynthesis: back to manganese

A nano-size amorphous calcium-manganese oxide shows efficient water oxidation activity in the presence of cerium(IV) ammonium nitrate.     

High-valent iron and manganese complexes of corrole and porphyrin in atom transfer and dioxygen evolving catalysis

Manganese(V) imido complexes of 5,10,15-tris(pentafluorophenyl)corrole (H(3)tpfc) can be prepared by the reaction of Mn(III)(tpfc) and organic nitrene generated from either photolytic or thermal activation of organic azides. The terminal imido complexes of manganese(V) were among the first structurally characterized examples of Mn(V) terminal imido complexes in the literature. They feature a short Mn≡N triple bond and a nearly linear M[triple bond, length as m-dash]N-C angle. The ground state of (tpfc)Mn(V)(NAr) is singlet. Contrary to expectations, arylimido complexes of manganese(V) were stable to moisture and did not undergo [NR] group transfer to olefins. Manganese(V) imido corrole with an activated tosyl imido ligand was prepared from iodoimine (ArINTs) and manganese(III) corrole. The resulting complex (tpfc)Mn(NTs) is paramagnetic (S = 1), hydrolyzes to (tpfc)Mn(O) in the presence of water, abstracts hydrogen atoms from benzylic C-H bonds, and catalyzes aziridination of alkenes. Mechanistic studies on the aziridination and hydrogen atom transfer reactions are reviewed. This perspective also describes the reaction chemistry of the heme enzyme chlorite dismutase, the mechanism by which dioxygen is formed on a single-metal site, and recent advances in functional modelling of this enzyme. We also compare the reactivity of water-soluble iron versus manganese porphyrins towards the chlorite anion.     

Lavandulifolioside B: a new phenylethanoid glycoside from the aerial parts of Stachys lavandulifolia Vahl

Reversed-phase preparative HPLC analyses of the methanol extract of the aerial parts of Stachys lavandulifolia afforded a new phenylethanoid glycoside, 4,3',4'-trimethoxy-lavandulifolioside A, named lavandulifolioside B, together with three other known phenylethanoid glycosides, lavandulifolioside A, verbascoside and leucosceptoside A, and an iridoid glycoside 5-O-β-allopyranosyloxy-aucubin (5-O-β-allopyranosyl-monomelittoside). While the structures of the known compounds, except the iridoid glycoside, were established by direct comparison of their spectroscopic data with respective literature data, lavandulifolioside B and 5-O-β-allopyranosyloxy-aucubin were identified comprehensively by extensive 1D and 2D NMR analyses. The distribution of the isolated compounds within the genus Stachys has been discussed.     

Nuclear data for the cyclotron production of 117Sb and 90Nb

This presented study is to make comparison of cross sections to produce 117Sb and 90Nb via different reactions with particle incident energy up to 70 MeV as a part of systematic studies on particle-induced activations on enriched Sn, Y2O3 and ZrO2 targets, theoretical calculation of production yield, calculation of required thickness of target and suggestion of optimum reaction to produce Antimony-117 and Niobium-90.     

Calcium manganese oxides as oxygen evolution catalysts: O2 formation pathways indicated by 18O-labelling studies

Oxygen evolution catalysed by calcium manganese and manganese-only oxides was studied in (18)O-enriched water. Using membrane-inlet mass spectrometry, we monitored the formation of the different O(2) isotopologues (16)O(2), (16)O(18)O and (18)O(2) in such reactions simultaneously with good time resolution. From the analysis of the data, we conclude that entirely different pathways of dioxygen formation catalysis exist for reactions involving hydrogen peroxide (H(2)O(2)), hydrogen persulfate (HSO(5)(-)) or single-electron oxidants such as Ce(IV) and [Ru(III) (bipy)(3)](3+) . Like the studied oxide catalysts, the active sites of manganese catalase and the oxygen-evolving complex (OEC) of photosystem II (PSII) consist of μ-oxido manganese or μ-oxido calcium manganese sites. The studied processes show very similar (18)O-labelling behaviour to the natural enzymes and are therefore interesting model systems for in vivo oxygen formation by manganese metalloenzymes such as PSII.     

A Hexagonally Ordered Nanoporous Silica-Based Fiber Coating for SPME of Polycyclic Aromatic Hydrocarbons from Water Followed by GC�CMS

A highly porous fiber coating material was prepared and functionalized with 3-amino propyl triethoxysilane (APTES) on hexagonally ordered nanoporous silica (SBA-15). Applicability of this coating was assessed employing a laboratory made solid-phase microextraction (SPME) device and gas chromatography?Cmass spectrometry for the simultaneous sampling and determination of trace polycyclic aromatic hydrocarbons (PAHs) from aqueous sample solutions. A one at the time optimization strategy was applied to investigate and optimize important extraction parameters such as extraction temperature, extraction time, ionic strength and sonication time. In the optimum conditions, the relative standard deviations for deionized water, spiked with selected PAHs were between 3.3 and 7.7% (n = 3), and detection limits for the studied compounds were 4.2 and 26.1 pg mL^?1. No significant change was observed in the extraction efficiency of the new SPME fiber, over 50 extractions. The proposed method was successfully applied to the extraction and determination of PAHs in the waste water samples.     

On the coupling of the homotopy perturbation method and Laplace transformation

In this paper, a Laplace homotopy perturbation method is employed for solving one-dimensional non-homogeneous partial differential equations with a variable coefficient. This method is a combination of the Laplace transform and the Homotopy Perturbation Method (LHPM). LHPM presents an accurate methodology to solve non-homogeneous partial differential equations with a variable coefficient. The aim of using the Laplace transform is to overcome the deficiency that is mainly caused by unsatisfied conditions in other semi-analytical methods such as HPM, VIM, and ADM. The approximate solutions obtained by means of LHPM in a wide range of the problem’s domain were compared with those results obtained from the actual solutions, the Homotopy Perturbation Method (HPM) and the finite element method. The comparison shows a precise agreement between the results, and introduces this new method as an applicable one which it needs fewer computations and is much easier and more convenient than others, so it can be widely used in engineering too.     

Centers on center manifolds in the Lü system

We confirm a conjecture of Mello and Coelho [Phys. Lett. A 373 (2009) 1116] concerning the existence of centers on local center manifolds at equilibria of the Lü system of differential equations on R³. Our proof shows that the local center manifolds are algebraic ruled surfaces, and are unique.     

Corrosion Inhibition of Mild Steel by Safflower (Carthamus tinctorius) Extract: Polarization,EIS, AFM,SEM, EDS,and Artificial Neural Network Modeling

Inhibitory action of safflower (Carthamus tinctorius) extract (SE) was investigated in hydrochloric acid solution through electrochemical (polarization, EIS), and surface analysis (optical microscopy/atomic force microscopy (AFM)/scanning electron microscopy (SEM)/energy dispersive spectroscopy (EDS)) techniques. In addition, Inhibition efficiency was predicted by neural network (NN) modeling in elevated temperatures and different acid concentrations. The thermodynamic adsorption parameters propose that this inhibitor retard both cathodic and anodic processes through physical adsorption and blocking the active corrosion sites. Surface analysis techniques confirm the inhibitor adsorption on the metal surface, which is in accordance with the variation of apparent activation energy of corrosion. Finally, inhibition efficiency is discussed in terms of protective film formation.