Interfacial Electrochemical Behavior of RuS2 Single Crystal Electrodes in Sulfuric Acid Medium

The electrochemical behavior of RuS₂ has been studied using cyclic voltammetry and Energy Dispersive X-ray Spectroscopy (EDX) techniques. Cyclic voltammograms reveal one major anodic peak and two major cathodic peaks on the reverse sweep; these peaks are attributed to the electroadsorption/desorption of OH^? groups on the electrode surface. It is proposed that the electroadsorption of the OH^? group on RuS₂ is due to the presence of Ru 4d electrons in the uppermost part of the valence band. Thus, OH^? is oxidized by holes on Ru 4d states in the first step. These groups are transferred to S₂^2?sites in the second step. EDX surface analysis reveals preferential release of S₂^2? from the pyrite lattice. A mechanism for the anodic dissolution of RuS₂ is proposed, according to which elemental sulfur is not a direct product, but rather the end product which forms from thiosulfate.     

Low temperature synthesis of bilayer hydrated cesium cobalt oxide

Bilayer hydrated Na_0.35CoO₂·1.3H₂O structure has re-directed superconductivity research in recent years. Here, we develop a low temperature synthesis method to prepare a novel hydrous Cs_0.2CoO₂·0.63H₂O compound in one step. The bilayer-hydrate of Cs_0.2CoO₂·0.63H₂O with a greatest interlayer spacing d=10.0(2) Å among alkali cobalt oxides has been grown in crystal form. Magnetic susceptibility measurement of Cs_0.2CoO₂·0.63H₂O displays a paramagnetic behavior down to 1.9 K. With the assistance of low temperature molten CsOH solvent, crystals of Rb_0.30CoO₂·0.36H₂O and K_0.35CoO₂·0.4H₂O can be grown. The results provide the capability for preparing a novel hydrous structure and the systematic investigation of interlayer coupling effect of alkali ion insertion compounds.     

Synthesis and Mossbauer Spectra Studies of Mono-Binuclear Iron(III) Complexes with a Quinquedentate Ligand Derived from Saucylaldehyeds and Diethylenetriamine

Mono- and bi-nuclear iron(III) complexes of general formula [FeXL] and [LFe-Y-FeL](Bph₄)₂ have been prepared, and their spin state of iron atom in the complexes has been studied by means of the temperature dependence of the Mössbauer spectra, electronic spectra and magnetic measurement, where X is a mono- dentate ligand such as Cl-, NCS-, NCO-, N3-, pyridine and L denotes a quinquedentate Schiff base derived from salicylaldehyde and diethylenetriamine, and Y denotes bridged ligand such as pyrazine(pyr), 4,4′-bipyridine(bpy) and 4,4′-vinylenebipyridine(vibpy). On the basis of the Mössbauer and magnetic data, it was concluded that these complexes were all the high-spin (S = 5/2) slate. The effect of gamma ray irradiation for these complexes has been discussed.     

E.S.R. of a one-dimensional Heisenberg antiferromagnet which undergoes a crystalline to discotic phase transition

Abstract

Single crystals and polycrystalline samples of the compounds bis(1,3-di(p-n-octylphenyl)propane-l,3-dionato)copper(II) [I], and bis(l,3-di(p-n-octyloxy-phenyl)propane-l,3-dionato)copper(II) [II] have been studied by E.S.R. The E.S.R. spectra of single crystals of [I] at 298 K have the features associated with a spin 1/2 one-dimensional Heisenberg antiferromagnet while the spectra of single crystals of [II] do not. E.S.R. of single crystals of [I] and [II] provides a reliable means of detecting previously reported crystalline to discotic phase transitions. Single crystals of [I] heated beyond the temperature of the first discotic phase transition yield single line E.S.R. spectra which have an angular dependence and an asymmetric lineshape; these observations suggest that, in the discotic phase, exchange interactions are still significant and a degree of long range order is maintained.     

A hybrid neuro-fuzzy analytical approach to mode choice of global logistics management

This paper presents a hybrid neuro-fuzzy methodology to identify appropriate global logistics (GL) operational modes used for global supply chain management. The proposed methodological framework includes three main developmental phases: (1) establishment of a GL strategic hierarchy, (2) formulation of GL-mode identification rules, and (3) development of a GL-mode choice model. By integrating advanced multi-criteria decision-making (MCDM) techniques including fuzzy analytical hierarchy process (Fuzzy-AHP), Fuzzy-MCDM, and the technique for order preference by similarity to an ideal solution (TOPSIS), six types of global logistics and operational modes coupled with corresponding fuzzy-based multi-criteria decision-making rules are specified in the second phase. Using the specified fuzzy decision-making rules as the input database, an adaptive neuro-fuzzy inference system (ANFIS) is then developed in the third phase to identify proper GL modes for the implementation of global supply chain management. A numerical study with a questionnaire survey database aimed at the information technology (IT) industries of Taiwan is conducted to illustrate the applicability of the proposed method.     

Electrical-optical analysis of a GaN/sapphire LED chip by considering the resistivity of the current-spreading layer

The effects of current distribution in LED chips on the electrical potential and optical light extraction efficiency are investigated by a numerical simulation. The results show that when the resistivity of the current-spreading layer is decreased there is current-crowding near the n-contact. On the other hand, when the resistivity in the current-spreading layer increases, there is current-crowding near the p-contact. When the current is crowded near the n-contact due to less resistivity of the current-spreading layer, the input power is lower because of the smaller series resistance in the chip, and the light extraction efficiency is higher since the shadowing effect of the p-contact can be avoided. For L _p = 50 μm in this study, the light extraction efficiency at ρ _ITO = 0.1 × 10⁻³ Ω·cm is 1.4 times better than that when L _p = 100 μm, even though the driving voltage is raised 1.02 times.     

Briaexcavatins A and B, novel briaranes from the octocoral Briareum excavatum

Two novel briaranoidal derivatives, designated as briaexcavatins A (1) and B (2), along with two known metabolites, excavatolides B and C (3 and 4), were isolated from the octocoral Briareum excavatum. Both compounds 1 and 2 possess unprecedented 5,6-epoxy moiety in the 10-membered ring. Diterpenoid 1 possesses a novel pentacyclic skeleton with a ε-lactone. The structures of diterpenoids 1 and 2 were elucidated by interpretation of spectral data and the absolute stereochemistry was established by application of modified Mosher’s method on 3.     

Ionic liquid of choline chloride/malonic acid as a solvent in the synthesis of open-framework iron oxalatophosphates

Two new iron(III) oxalatophosphates, Cs2Fe(C2O4)(0.5)(HPO4)2 (1) and CsFe(C2O4)(0.5)(H2PO4)(HPO4) (2), have been synthesized by using a low melting point eutectic mixture of choline chloride and malonic acid as a solvent and characterized by single-crystal X-ray diffraction and magnetic susceptibility. Crystal data are as follows: compound 1, monoclinic, P2(1)/c (No. 14), a = 8.5085(4) A, b = 12.7251(6) A, c = 9.8961(4) A, beta = 107.117(1) degrees , V = 1024.01(8) A(3), Z = 4, and R(1) = 0.0264; compound 2, monoclinic, P2(1)/n (No. 14), a = 8.0038(3) A, b = 10.2923(3) A, c = 11.4755(4) A, beta = 100.507(1) degrees , V = 929.47(5) A(3), Z = 4, and R(1) = 0.0311. The structure of 1 comprises FeO6 octahedra connected by HPO4(2-) tetrahedra and bisbidentate oxalate anions to form a 3D framework containing intersecting 12-ring channels, with the charge-compensating Cs+ cations being located at the intersections of these channels. The structure of 2 consists of 2D layers of octahedral FeO6, tetrahedral H2PO4- and HPO4(2-) moieties, and bisbidentate oxalate ligands with the Cs+ cations between the layers. They are the first examples for the use of ionic liquid as a solvent in the synthesis of metal oxalatophosphates.     

Carbon dioxide fixation by an unprecedented hydroxo lead-chromium carbonyl complex: synthesis, reactivity, and theoretical calculations

The novel hydroxo-bridged dimeric lead-chromium carbonyl complex [Et4N]2[{PbCr2(CO)10}2(mu-OH)2] ([Et4N]2[1]) was synthesized from the reaction of PbCl2 and Cr(CO)6 followed by metathesis with [Et4N]Br in a KOH/MeOH solution. The X-ray crystallographic structure shows that dianion 1 consists of two Pb{Cr(CO)5}2 units bridged by two hydroxo fragments in which the Pb atoms are further coordinated with two Cr(CO)5 groups, resulting in a distorted tetrahedral geometry. A CO2 molecule can insert itself into dianion 1 to form two new carbonate complexes, [Et(4)N]2[{PbCr2(CO)10}(CO3)] ([Et4N]2[2]) and [Et4N]2[{PbCr2(CO)10}2(CO3)] ([Et4N]2[3]), depending on the reaction conditions. In addition, complex 2 can be transformed into 3 in CH2Cl2 solution at an elevated temperature. While the carbonate group in dianion 2 is bonded to one Pb atom, which is coordinated with two Cr(CO)5 fragments, the carbonate group in 3 bridges the two Pb centers in a mu-1kappa2OO':2kappa2OO' fashion in which each Pb atom is further bonded to two Cr(CO)5 moieties. Complexes 2 and 3 can be converted back the hydroxo complex 1 under appropriate conditions. All three unprecedented lead-chromium compounds, 1-3, were fully characterized by spectroscopic methods and single-crystal X-ray diffraction analyses. The nature and formation of complexes 1-3 were also examined by molecular orbital calculations using the B3LYP method of the density functional theory.