A porphyrin bearing tetrahydrothiophene pickets; co-ordination behaviour and electron transfer

A novel ‘picket-fence’ porphyrin, 5,10,15,20-tetrakis[o-(tetrahydro-2-thenoylamino)phenyl]porphyrin (H2L) with ligating tetrahydrothiophene rings disposed perpendicular to the porphyrin plane has been synthesised. Its zinc(II) derivative, [ZnL], binds two silver(I) ions co-operatively with a dissociation constant of 4.8 × 10–8 dm3 mol–1. Time-resolved fluorescence lifetime measurements reveal the presence of intramolecular photoexcited electron transfer in this donor–acceptor system.

Electron energy loss spectroscopic study of Cr(CO)6, Mo(CO)6 and W(CO)6 in the vapour phase

Electron energy loss spectra (EELS) of Cr, Mo and W hexacarbonyls in the vapour phase are reported. Most of the bands observed are similar to those in optical spectra, but the two high energy transitions in the 9·8–11·2 eV region are reported here for the first time. Based on the orbital energies from the ultraviolet photoelectron spectra and the electronic transition energies from EELS and earlier optical studies, the molecular energy level schemes of these molecules are constructed.

Chemical toughening of epoxies. II. Mechanical, thermal, and microscopic studies of epoxies toughened with hydroxyl-terminated poly(butadiene-co-acrylonitrile)

Diglycidyl ether–bisphenol-A-based epoxies toughened with various levels (0–12%) of chemically reacted liquid rubber, hydroxyl-terminated poly(butadiene-co-acrylonitrile) (HTBN) were studied for some of the mechanical and thermal properties. Although the ultimate tensile strength showed a continuous decrease with increasing rubber content, the toughness as measured by the area under the stress-vs.-strain curve and flexural strength reach a maximum around an optimum rubber concentration of 3% before decreasing. Tensile modulus was found to increase for concentrations below 6%. The glass transition temperature Tg as measured by DTA showed no variation for the toughened formulations. The TGA showed no variations in the pattern of decomposition. The weight losses for the toughened epoxies at elevated temperatures compare well with that of the neat epoxy. Scanning electron microscopy revealed the presence of a dual phase morphology with the spherical rubber particles precipitating out in the cured resin with diameter varying between 0.33 and 6.3 μm. In contrast, a physically blended rubber–epoxy showed much less effect towards toughening with the precipitated rubber particles of much bigger diameter (0.6–21.3 μm).

Chemical toughening of epoxies. I. Structural modification of epoxy resins by reaction with hydroxy-terminated poly(butadiene-co-acrylonitrile)

In an attempt to toughen the epoxy resin matrix for fiber-reinforced composite applications, a chemical modification procedure of a commercially available bisphenol-A-based epoxy resin using reactive liquid rubber HTBN [hydroxy-terminated poly(butadiene-co-acrylonitrile)] and TDI (tolylene diisocyanate) is described. The progress of the reaction and the structural changes during modification process are studied using IR spectroscopy, viscosity data, and chemical analysis (epoxy value determination). The studies support the proposition that TDI acts as a coupling agent between the epoxy and HTBN, forming a urethane linkage with the former and an oxazolidone ring with the latter. The chemical reactions that possibly take place during the modification are discussed.

Organometallic chemistry of diphosphazanes *1: VIII. Synthesis, spectroscopic studies and crystal structure of fac-[Mo(CO)3(MeCN)Ph2PN(iPr)P(Ph)(DMP)], and its reactions with tertiary phosphines

The reaction of fac-[Mo(CO)3(MeCN)3] with the unsymmetrical diphosphazane Ph2PN(iPr)P(Ph)(DMP) (L) gives the complex fac-[Mo(CO)3(MeCN)(L)] (2) in almost quantitative yield. The structure of the complex has been determined by an X-ray diffraction study. The compound reacts with PR3 (where R = Ph, OPh) to give fac-[Mo(CO)3(PR3)(L)] (3a, 4a), which undergoes an intramolecular isomerization to afford mer-[Mo(CO)3(PR3)(L)] (3b, 4b). Synthesis of cis-[Mo(CO)4(L)] (1) and fac-[MO(CO)3L] (2a) and their spectroscopic data are also reported.

Making Sense of Value and Value Co-Creation in Service Logic

In order to further develop the logic of service, value creation, value co-creation and value have to be formally and rigorously defined, so that the nature, content and locus of value and the roles of service providers and customers in value creation can be unambiguously assessed. In the present article, following the underpinning logic of value-in-use, it is demonstrated that in order to achieve this, value creation is best defined as the customer’s creation of value-in-use. The analysis shows that the firm’s and customer’s processes and activities can be divided into a provider sphere, closed for the customer, and a customer sphere, closed for the firm. Value creation occurs in the customer sphere, whereas firms in the provider sphere facilitate value creation by producing resources and processes which represent potential value or expected value-in use for their customers. By getting access to the closed customer sphere, firms can create a joint value sphere and engage in customers’ value creation as co-creators of value with them. This approach establishes a theoretically sound foundation for understanding value creation in service logic, and enables meaningful managerial implications, for example as to what is required for co-creation of value, and also further theoretical elaborations.

Electron-beam irradiation effects on poly(ethylene-co-vinyl acetate) polymer

Poly(ethylene-co-vinyl acetate) (EVA) films were irradiated with a 1.2MeV electron beam at varied doses over the range 0-270kGy in order to investigate the modifications induced in its optical, electrical and thermal properties. It was observed that optical band gap and activation energy of EVA films decreased upon electron irradiation, whereas the transition dipole moment, oscillator strength and number of carbon atoms per cluster were found to increase upon irradiation. Further, the dielectric constant, the dielectric loss, and the ac conductivity of EVA films were found to increase with an increase in the dose of electron radiation. The result further showed that the thermal stability of EVA film samples increased upon electron irradiation.

Study of interdiffusion and growth of topologically closed packed phases in the Co-Nb system

Interdiffusion study of the Co-Nb system is conducted to determine the diffusion parameters in different phases. The integrated diffusion coefficients at different temperatures are calculated for the Nb2Co7 phase, which has very narrow composition range. The interdiffusion coefficients at different compositions in the NbCo2 Laves phase are determined. The interdiffusion coefficient in this phase decreases with increasing Nb content to the stoichiometric composition. Further, the average interdiffusion coefficient in the N6Co7-mu phase is determined. The activation energies for diffusion in different phases are calculated, providing valuable information regarding the diffusion mechanism. In addition, an experiment using Kirkendall markers is conducted to calculate the relative mobilities of the species.

Interdiffusion study on Co(W) solid solution and topological close-packed mu phase in Co-W system

An interdiffusion study is conducted on the Co-W system by a diffusion couple technique. The interdiffusion coefficient of the Co(W) solid solution and the Co7W6 mu phase is determined. The activation energy is found to increase with the W content of the Co(W) solid solution. (C) 2010 Elsevier Ltd. All rights reserved.

A study of cubic bismuth oxides of the type bi(26-X)m(X)O(40-delta) (m=ti, mn, fe, co, ni or pb) related to gamma-bi2O3

A structural investigation of cubic oxides (space group I23) of the formula Bi(26-x)M(x)O(40-delta) (M = Ti, Mn, Fe, Co, Ni and Pb) related to the Y-Bi2O3 phase has been carried out by the Rietveld profile analysis of high-resolution X-ray powder diffraction data in order to establish the cation distributions. Compositional dependence of the cation distribution has been examined in the case of Bi26-xCoxO40-delta (1 < x < 16). The study reveals that in Bi(26-X)M(X)O(40-delta) with M = Ti, Mn, Fe, Co or Pb, the M cations tend to occupy tetrahedral (2a) sites when x < 2 while the octahedral (24f) sites are shared by the excess Co or Ni cations with Bi atoms when x > 2. Also experimental magnetic moments of Mn, Co and Ni derivatives have been used to establish the valence state and distribution of these cations.

Diffusion path during internal displacement reactions in multi-component oxides: Reaction between Fe and (Co,Mg)TiO3 solid solution at 1273 K

The reaction between Fe foil and a disc of ilmenite solid solution (Co-0.48 Ni-0.52) TiO3 was studied at 1273 K. At the metal/oxide interface, the displacement reaction, Fe + (Co,Mg)TiO3 = Co + (Fe,Mg)TiO3 occurs, resulting in an ilmenite solid solution containing three divalent cations. Ferrous ions diffuse into the oxide solid solution and cause the precipitation of Co-Fe alloy as discrete particles inside the oxide matrix. The morphology of the product layer was characterized by SEM. Only two phases, alloy and ilmenite, were detected in the reaction zone. This suggests that the local flux condition imposed by ilmenite stoichiometry (Co + Fe + Mg):Ti = 1:1] was satisfied during the reactive diffusion: (J(Co) + J(Fe) + J(Mg)) = J(Ti). The composition of the alloy and the oxide was determined using EPMA as a function of distance in the direction of diffusion. Although Mg does not participate in the displacement reaction, its composition in the ilmenite phase was found to be position dependent inside the reaction zone. The up-hill diffusion of inert Mg is caused by the development of chemical potential gradients as a result of displacement reaction. The evolution of composition gradients inside the reaction zone and the diffusion path in a ternary composition diagram of the system CoTiO3-FeTiO3-MgTiO3 are discussed. (C) 2010 Elsevier B.V. All rights reserved.

Synthon polymorphism and pseudopolymorphism in co-crystals. The 4,4 `-bipyridine-4-hydroxybenzoic acid structural landscape

Co-crystals of 4,4'-bipyridine and 4-hydroxybenzoic acid (1 : 2) show synthon polymorphism with the former being more stable. A 2 : 1 co-crystal is pseudopolymorphic within the same structural landscape with the structural roles of the two bipyridine N-atoms being distinct, as evidenced by mimicry by 4-phenylpyridine.

Temperature-programmed desorption and surface reaction of thiophene over co-mo/.gamma.-Al2O3 hydrodesulfurization catalysts

The temperature-programmed desorption (TPD) and temperature-programmed surface reaction (TPSR) of thiophene over a series of Co-Mo/gamma-Al2O3, hydrodesulfurization (HDS) catalysts with varying Co to Mo ratios have been studied with the objective of understanding the promotional role of Co in the HDS reaction. As part of the study, the desorptions (TPD) and hydrogenations (TPSR) of butane, butene, and butadiene over these catalysts have also been investigated. The TPD of the hydrocarbons over catalysts containing no Co showed a single desorption profile while incorporation of Co created an additional site, with higher heats of desorption, without significantly affecting desorption from the original site. The TPSR measurements showed that the two sites had separate and independent activity for the hydrogenation of the C-4 hydrocarbons. The TPD of thiophene over catalysts with varying Co to Mo ratios showed a single desorption profile with identical heats of desorption, implying that Co does not affect or influence the adsorption sites for thiophene. The TPSR of the HDS of thiophene, however, showed that, although the products of the HDS reaction-butane, butene, and H2S-are the same irrespective of the Co content, the temperature profiles and the activation barriers for the formation of these species show considerable change with the Co/Co+Mo ratio. The results are discussed in light of the existing models for the promotional role of Co in the HDS reaction.

A comparative study of the interaction of CO with Cu and Cu-Zn alloy clusters

Interaction of CO with Cu clusters deposited on a ZnO(0001) crystal and on ZnO/Zn surfaces (prepared in the electron spectrometer) has been examined by UV and X-ray photoelectron spectroscopy. The interaction is stronger with the small Cu clusters deposited on ZnO/Zn surfaces. Interaction of CO is evert stronger with annealed Cu/ZnO/Zn surfaces where Cu-Zn alloy particles are present. Copyright (C) 1996 Published by Elsevier Science Ltd