On the synthesis and structures of the complexes [RuCl(L)(dppb)(N-N)]PF(6) (L = CO, py or 4-NH(2)py; dppb=1,4-bis(diphenylphosphino)butane; N-N=2,2 `-bipyridine or 1,10-phenanthroline) and [(dppb)(CO)Cl(2)-Ru-pz-RuCl(2)(CO)(dppb)] (pz = pyrazine)

The ""Ru(P-P)"" unit (P-P = diphosphine) is recognized to be an important core in catalytic species for hydrogenation of unsaturated organic substrates. Thus, in this study we synthesized six new complexes containing this core, including the binuclear complex [(dppb)(CO)Cl(2)Ru-pz-RuCl(2)(CO)(dPPb)] (pz = pyrazine) which can be used as a precursor for the synthesis of cationic carbonyl species of general formula [RuCl(CO)(dppb)(N-N)]PF(6) (N-N = diimine). Complexes with the formula (RuCl(py)(dppb)(N-N)]PF(6) were synthesized by exhaustive electrolysis of these carbonyl compounds or from the precursors [RuCl(2)(dppb)(N-N)]. The new complexes were characterized by microanalysis, conductivity measurements, IR and (31)P{(1)H)} NMR spectroscopy, cyclic voltammetry and X-ray crystallography. (C) 2010 Elsevier Ltd. All rights reserved.

Synthesis, characterization and cytotoxic activities of the [RuCl(2)(NO)(dppp)(L)]PF(6) complexes

The synthesis and characterization of ruthenium compounds of the type [RuCl(2)(NO)(dppp)(L)]PF(6) [dppp = 1,3-bis(diphenylphosphino)propane; L = pyridine, 4-methylpyridine, 4-phenylpyridine and dimethyl sulfoxide] are described. The complexes were characterized by elemental analysis, UV/Vis and infrared spectroscopy, cyclic voltammetry, and X-ray crystallography for the complexes with the pyridine and 4-methylpyridine ligands. In vitro evaluation of these nitrosyl complexes revealed cytotoxic activity from 7.1 to 19.0 mu M against the MDA-MB-231 breast tumor cells and showed that, in this case, they are more active than the reference metallodrug cisplatin. The 1,3-bis(diphenylphosphino)propane and the N-heterocyclic ligands alone failed to show cytotoxic activities at the concentrations tested (maximum concentration utilized = 200 mu M). (C) 2009 Elsevier Inc. All rights reserved.

Polymethine cyanine dyes in beta-cyclodextrin solution: multiple equilibria and chemical oxidation

Absorption and fluorescence spectroscopy, electrochemical techniques, and semiempirical calculations were employed to characterize the multiple complexation equilibria between two polymethine cyanine dyes (IR-786 and Indocyanine green-ICG, 5) and beta-cyclodextrin (beta-CD, L), as well as the chemical reactivity of the complexed and uncomplexed species against the oxidizing agents hypochlorite (HC) and hydrogen peroxide (HP). IR-786 dimerization is favored with the increase in beta-CD concentration in the form of (SL)(2) complexes. In the case of ICG, free dimers (D) and SL complexes are favored. Both IR-786 and ICG react and discolor in the presence of HC and HP. For IR-786, the reaction with HP and HC proceeds with observed rate constants of 10(-3) and 0.28 s(-1) and second-order rate constants (k(2)) of similar to 10(-3) and 10(4) M(-1) s(-1), respectively. The intermediate species observed in the bleaching reactions of IR-786 and ICG were shown, by cyclic voltammetry and VIS absorption, to result from one electron oxidation. IR-786 complexed with beta-CD is protected against bleaching in the presence of HP and HC by factors of 20 and 4, respectively. This protection was not observed in ICG complexes. Superdelocalizability profile of both dyes and frontier orbital analysis indicates that beta-CD does not protect ICG from oxidation by HP or HC, whereas the 2:2 IR-786/beta-Cd complex is able to avoid the oxidation of IR-786. We concluded that the decrease in the chemical reactivity of the dyes against oxidant agents in the presence of beta-CD is due to the formation of (SL)(2) complexes. Copyright (C) 2010 John Wiley & Sons, Ltd.

Lithium Ion Electro-Insertion and Spectroelectrochemical Properties of Films from Hexaniobate

Layer-by-layer (LbL) films from K(2)Nb(6)O(17)(2-) and polyallylamine (PAH) and dip-coating films of H(2)K(2)Nb(6)O(17) were prepared on a fluorine-doped tin-oxide (FTO)-coated glass. The atomic force microscopy (AFM) images were carried out for morphological characterization of both materials. The real surface area and the roughness factor were determined on the basis of pseudocapacitive processes involved in the electroreduction/electrooxidation of gold layers deposited on these films. Next, lithium ion insertion into these materials was examined by means of electrochemical and spectroelectrochemical measurements. More specifically, cyclic voltammetry and current pulses under visible light beams were used to investigate mass transport and chromogenic properties. The lithium ion diffusion coefficient (D(Li)) within the LbL matrix is significantly higher than that within the dip-coating film, ensuring high storage capacity of lithium ions in the self-assembled electrode. Contrary to the LbL film, the potentiodynamic profile of absorbance change (Delta A) as a function of time is not similar to that obtained in the case of current density for the dip-coating film. Aiming at analyzing the rate of the coloration front associated with lithium ion diffusion, a spectroelectrochemical method based on the galvanostatic intermittent titration technique (GITT) was employed so as to determine the ""optical"" diffusion coefficient (D(op)). In the dip-coating film, the method employed here revealed that the lithium ion rate is higher in diffusion pathways formed from K(2)Nb(6)O(17)(2-) sites that contribute more significantly to Delta A. Meanwhile, the presence of PAH contributed to the increased ionic mobility in diffusion pathways in the LbL film, with low contribution to the electrochromic efficiency. These results aided a better understanding of the potentiodynamic profile of the temporal change of absorbance and current density during the insertion/deinsertion of lithium ions into the electrochromic materials.

Electrocatalytic behavior of glassy carbon electrodes modified with multiwalled carbon nanotubes and cobalt phthalocyanine for selective analysis of dopamine in presence of ascorbic acid

This work describes the development, electrochemical characterization and utilization of a cobalt phthalocyanine modified carbon nanotube electrode for the quantitative determination of dopamine in 0.2 mol L-1 phosphate buffer contaminated with high concentration of ascorbic acid. The electrode surface was analyzed by cyclic voltammetry and electrochemical impedance spectroscopy which showed a modified surface presenting a charge transfer resistance of 500 Omega, against the 16.46 k Omega value found for the bare glassy carbon surface. A pseudo rate constant value of 5.4 x 10(-4) cm s(-1) for dopamine oxidation was calculated. Voltammetric experiments showed a shift of the peak potential of DA oxidation to less positive value at 390 mV as compared with that of a bare GC electrode at 570 mV. The electrochemical determination of dopamine, in presence of ascorbic acid in concentrations up to 0.1 mol L-1 by differential pulse voltarnmetry, yielded a detection limit as low as 2.56 x 10(-7) mol L-1.

Electrocatalysis of ethanol oxidation on Pt monolayers deposited on carbon-supported Ru and Rh nanoparticles

Pt monolayers deposited on carbon- supported Ru and Rh nanoparticles were investigated as electrocatalysts for ethanol oxidation. Electronic features of the Pt monolayers were studied by in situ XANES (X-ray absorption near-edge structure). The electrochemical activity was investigated by cyclic voltammetry and cronoamperometric experiments. Spectroscopic and electrochemical results were compared to those obtained on carbon-supported Pt-Ru and Pt-Rh alloys, and Pt E-TEK. XAS results indicate a modification of the Pt 5d band due to geometric and electronic interactions with the Ru ant Rh substrates, but the effect of withdrawing electrons from Pt is less pronounced in relation to that for the corresponding alloys. Electrochemical stripping of adsorbed CO, which is one of the intermediates, and the currents for the oxidation of ethanol show faster kinetics on the Pt monolayer deposited on Ru nanoparticles, and an activity that exceeds that of conventional catalysts with much larger amounts of platinum. (c) 2007 Elsevier B.V. All rights reserved.

Influence of microstructure on strain distribution in Mg–3Al–1Zn

Inspection of pre-polished surfaces of Mg–3Al–1Zn hot-rolled plate following 5% uniaxial compression revealed a distinctive heterogeneous deformation pattern. The pattern differed depending on the face examined. The greater share of the strain was born by regions characterized by grains considerably finer than the average. These regions displayed a favourable alignment for basal slip and were probably formed by shear banding during previous rolling. It is clear that local orientation softening leads to inhomogeneous deformation despite local grain size-hardening and twin activation.

Development and applications of an experimental database for structural engineering education

A great number of research organisations in Japan have been conducting structural steel experiments for many years, particularly seismic tests of steel structures like cyclic-loading and pseudo-dynamic tests, in order to determine their seismic performances. However, the original test data gained by most research organisations are not well stored in an appropriate manner for distribution and possible usage by others. With the rapid development of information networks, structural engineers and researchers are able to exchange various types of test data through the Internet. In this paper, the authors present the development of a distributed collaborative database system for structural steel experiments. The database is made available on the Internet, and the use of Java language enables efficient interactive retrieval. The potential applications of the developed database system for structural engineering education are validated for the retrieval of experimental data and seismic numerical analysis.

Development and application of a microelectrode based scanning voltammetric detector

A large part of the work presented in this thesis describes the development and use of a novel electrochemical detector designed to allow the electrochemical characterisation of compounds in flowing solution by means of cyclic voltammetry. The detector was microprocessor controlled, which provides digital generation of the potential waveform and collection of data for subsequent analysis. Microdisk working electrodes are employed to permit both thermodynamic and kinetically controlled processes to be studied under steady-state conditions in flowing solutions without the distortion or hysteresis normally encountered with larger sized electrodes. The effect of electrode size, potential scan rate, and solution flow rate are studied extensively with the oxidation of ferrocene used as an example of a thermodynamically controlled process and a series of catecholamines as examples of a kinetically controlled process. The performance of the detector was best demonstrated when used as a HPLC post-column detector. The 3-dimensional chromatovoltammograms obtained allow on-line characterisation of each fraction as it elutes from the column. The rest of the work presented in this thesis involves the study of the oxidative degradation pathway of dithranol. The oxidative pathway was shown to involve a complex free radical mechanism, dependent on the presence of both oxygen and, in particular light. The pathway is further complicated by the fact that dithranol may exist in either a keto or enol form, the enol being most susceptible to oxidation. A likely mechanism is proposed from studies performed with cyclic voltammetry and controlled potential electrolysis, then defined by subsequent kinetic studies.

Microstructure evolution modeling during and after deformation in 304 austenitic stainless steel through cellular automaton approach

A 2D cellular automation approach was used to simulate microstructure evolution during and after hot deformation. Initial properties of the microstructure and dislocation density were used as input data to the cellular automation model. The flow curve and final grain size were the output data for the dynamic recrystallization simulation, and softening kinetics curves were the output data of static and metadynamic recrystallization simulations. The model proposed in this work considered the effect of thermomechanical parameters (e.g., temperature and strain rate) on the nucleation and growth kinetics during dynamic recrystallization. The dynamic recrystallized microstructures at different strains, temperatures, and strain rates were used as input data for static and metadynamic recrystallization simulations. It was shown that the cellular automation approach can model the final microstructure and flow curve successfully in dynamic recrystallization conditions. The postdeformation simulation results showed that the time for 50% recrystallization decreases with increasing strain for a given initial grain size and that dynamic recrystallization slows the postdeformation recrystallization kinetics compared to a model without dynamic recrystallization.

Physical trends and structural features in organic salts of the thiocyanate anion

A new series of ionic liquids based on the thiocyanate anion has been prepared. Incorporation of this anion with an imidazolium, tetraalkylammonium or pyrrolidinium cation produces ionic liquids with advantageously low melting points and good thermal stability. The low temperature phase behaviour of the salts has been investigated using differential scanning calorimetry and multiple solid phases have been observed. The electrochemical windows of representative imidazolium and pyrrolidinium species have been investigated by cyclic voltammetry and determined to be 2.4 and 3.5 V, respectively. In addition, the solid-state structure of N,N-dimethylpyrrolidinium thiocyanate has been determined by X-ray crystallography. This is the first reported structure of a pyrrolidinium thiocyanate species and shows a layered structure with linear thiocyanate groups having bond lengths comparable to those observed in similar SCN−-containing species.

Effect of tool speeds during friction stir lap welding on mode of fracture and fracture strength of Al 6060-T5 joints

Friction stir lap welding (FSLW) of an age hardened Al alloy and evaluations of how FS speeds affected hooking and how hooking and softening due to FS affected fracture strength of the lap welds have been conducted. It was found that increasing rotation speed and reducing welding speed (v) increased the stir zone size (AB-SZ) and also hook size (h), although a maximum value of h (hMax) reached. The features of hooks for the observed - AB-SZ-h relationships are presented and explained. It was found that when h increased to a value of ~ 0.9 mm (for the 3 mm alloy sheets), it started to invoke a significant effect on reducing fracture strength. Factors such as FS softening and insufficient joining, limited the fracture strength of the lap welds for small h values and these are presented and discussed.

Solving the median shortest path problem in the planning and design of urban transportation networks using a vector labeling algorithm

This paper proposes an alternative algorithm to solve the median shortest path problem (MSPP) in the planning and design of urban transportation networks. The proposed vector labeling algorithm is based on the labeling of each node in terms of a multiple and conflicting vector of objectives which deletes cyclic, infeasible and extreme-dominated paths in the criteria space imposing cyclic break (CB), path cost constraint (PCC) and access cost parameter (ACP) respectively. The output of the algorithm is a set of Pareto optimal paths (POP) with an objective vector from predetermined origin to destination nodes. Thus, this paper formulates an algorithm to identify a non-inferior solution set of POP based on a non-dominated set of objective vectors that leaves the ultimate decision to decision-makers. A numerical experiment is conducted using an artificial transportation network in order to validate and compare results. Sensitivity analysis has shown that the proposed algorithm is more efficient and advantageous over existing solutions in terms of computing execution time and memory space used.

Fabrication, microstructure and mechanical properties of high performance ferrite-bainite steels

Low cost ferrite and bainite(FB) steels offer the prospect of high ultimate tensile strength combined with high hole expansion ratio. The enhanced strain hardening and formabilityof FB steels were primarily associated with the fine ferrite matrix, the low residual stresses and dislocation densityand compatible deformation between both phases.This overview describes the various techniques to produce FB steels, and comparestheresulting microstructure, tensile propertiesand tretchflangeabilitywith conventional HSLA and DP steels.A new generation of ultrafine ferrite and nano-scalebainiteautomotive steelsisunder development forthe futuredemands of extremely high strength and ductilitythroughthe fabricationtechnologiesinvolvingphase transformationsandplastic deformation.

Evolution of the electrochemical capacitance of transition metal oxynitrides with time: the effect of ageing and passivation

A number of transition metal nitrides and oxynitrides, which are actively investigated today as electrode materials in a wide range of energy conversion and storage devices, possess an oxide layer on the surface. Upon exposure to ambient air, properties of this layer progressively change in the process known as "ageing". Since a number of electrochemical processes involve the surface or sub-surface layers of the active electrode compounds only, ageing could have a significant effect on the overall performance of energy conversion and storage devices. In this work, the influence of the ageing of tungsten and molybdenum oxynitrides on their electrochemical properties in supercapacitors is explored for the first time. Samples are synthesised by the temperature-programmed reduction in NH3 and are treated with different gases prior to exposure to air in order to evaluate the role of passivation in the ageing process. After the synthesis, products are subjected to controlled ageing and are characterised by low temperature nitrogen adsorption, X-ray photoelectron spectroscopy and transmission electron microscopy. Capacitive properties of the compounds are evaluated by performing cyclic voltammetry and galvanostatic charge and discharge measurements in the 1 M H2SO4 electrolyte. © 2014 the Partner Organisations.