Synthesis,crystal structure and catalytic activity for H2O2 disproportionation of the manganese(II) coordination polymer {[Mn(O2C(CF2)8CO2)(phen)2]H2O}n (phen = 1,10-phenanthroline)

The title polymeric complex {[Mn(O₂C(CF₂)₈CO₂)(phen)₂]H₂O}_n was synthesized through the reaction of 1,10-phenanthroline, perfluorosebacic acid and MnCO₃ · H₂O. The molecular structure was characterized by X-ray diffraction, elemental analysis, thermal gravimetry, IR and UV–Vis spectroscopy and its catalytic activity has been studied. X-ray structure analysis shows that each Mn(II) ion is octahedrally coordinated by two bidentate phenanthroline ligands and the carboxylate oxygen atoms from two symmetry related perfluorosebacate ligands, which are coordinated in cisoid positions. The structure consists of polymeric chains, with the perfluorosebacato ligand bridging the Mn(II) ions in a monodentate fashion. Crystallographic characterization shows a supramolecular structure involving hydrogen bonds, π–π and π-ring interactions. The catalytic results indicated that the complex has reasonably good activity towards the disproportionation of hydrogen peroxide into water and dioxygen in methanol and it does not exhibit saturation kinetics with the substrate. The initial reaction rates and their temperature and base dependencies were investigated by monitoring the dioxygen evolution. Kinetic studies revealed a first-order dependence on the catalyst concentration. Activation parameters have been calculated at 301 K.     

The properties of the new Mn(II)–Co(II)–Mn(II)-type hetero-trinuclear oxime metal complexes with N4 and N4O2 ligands

1,3- and 1,2-calix[4]crown-7 and calix[4]crown-9 cone conformers were synthesized in acceptable yields by sequential introduction of two distal or proximal polyethylene glycolic chains with terminal hydroxyls at the lower rim, monotosylation, and intramolecular ring closure reaction. According to the two-phase extraction experiment, the title compounds showed mediocre affinity for alkali and alkaline earth metal picrates. The 1,2-calix[4]crown-9 extracted Sr²⁺ selectively among other alkaline earth metal cations.     

Fourier optics analysis of grating sensors with tilt errors

Dynamic diffraction gratings can be microfabricated with precision and offer extremely sensitive displacement measurements and light intensity modulation. The effect of pure translation of the moving part of the grating on diffracted order intensities is well known. This study focuses on the parameters that limit the intensity and the contrast of the interference. The effects of grating duty cycle, mirror reflectivities, sensor tilt and detector size are investigated using Fourier optics theory and Gaussian beam optics. Analytical findings reveal that fringe visibility becomes <0.3 when the optical path variation exceeds half the wavelength within the grating interferometer. The fringe visibility can be compensated by monitoring the interfering portion of the diffracted order light only through detector size reduction in the expense of optical power. Experiments were conducted with a grating interferometer that resulted in an eightfold increase in fringe visibility with reduced detector size, which is in agreement with theory. Findings show that diffraction grating readout principle is not limited to translating sensors but also can be used for sensors with tilt or other deflection modes.     

Spectral amplitude and phase measurement of ultrafast pulses using all-optical differential tomography

We demonstrate a simple, all-optical, fiber-based method for characterizing the spectral amplitude and phase of ultrafast pulses using a differential tomographic measurement realized via four-wave mixing. The technique is applied to subpicosecond pulses in the C-band of the telecommunication spectrum. Characterization of amplified pulses and propagation through dispersive media is demonstrated and compared with autocorrelation measurements and calculated predictions. We show how our approach can be extended to larger bandwidths in similar systems, extending tomographic reconstruction of coherent fields to nearly an octave of bandwidth while maintaining a robust, waveguide-based geometry.     

Selling to the “Newsvendor” with a forecast update: Analysis of a dual purchase contract

We consider a supply chain in which a manufacturer sells to a procure-to-stock retailer facing a newsvendor problem with a forecast update. Under a wholesale price contract, the retailer waits as long as she can and optimally places her order after observing the forecast update. We show that the retailer’s wait-and-decide strategy, induced by the wholesale price contract, hinders the manufacturer’s ability to (1) set the wholesale price and maximize his profit, (2) hedge against excess inventory risk, and (3) reduce his profit uncertainty. To mitigate the adverse effect of wholesale price contract, we propose the dual purchase contract, through which the manufacturer provides a discount for orders placed before the forecast update. We characterize how and when a dual purchase contract creates strict Pareto improvement over a wholesale price contract. To do so, we establish the retailer’s optimal ordering policy and the manufacturer’s optimal pricing and production policies. We show how the dual purchase contract reduces profit variability and how it can be used as a risk hedging tool for a risk averse manufacturer. Through a numerical study, we provide additional managerial insights and show, for example, that market uncertainty is a key factor that defines when the dual purchase contract provides strict Pareto improvement over the wholesale price contract.     

A fuzzy goal programming method with imprecise goal hierarchy

Two most widely used approaches to treating goals of different importance in goal programming (GP) are: (1) weighted GP, where importance of goals is modelled using weights, and (2) preemptive priority GP, where a goal hierarchy is specified implying infinite trade-offs among goals placed in different levels of importance. These approaches may be too restrictive in modelling of real life decision making problems. In this paper, a novel fuzzy goal programming method is proposed, where the hierarchical levels of the goals are imprecisely defined. The imprecise importance relations among the goals are modelled using fuzzy relations. An additive achievement function is defined, which takes into consideration both achievement degrees of the goals and degrees of satisfaction of the fuzzy importance relations. Examples are given to illustrate the proposed method.     

Transient heat conduction with uniform heat generation in a slab subjected to convection and radiation cooling

A finite difference scheme with fourth order Runge-Kutta method is employed to determine the unsteady state temperature distribution in a plane slab with uniform heat generation. The plane slab is insulated on one face and subjected to convective and radiative cooling at the other face. The plane slab has a uniform initial temperature and the ambient environment as well as the fluid temperatures are assumed to be constant. Heat conduction is considered to be one dimensional. Results are presented in dimensionless charts over a wide range of parameters.

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Instationäre Wärmeleitung mit gleichförmiger Wärmeerzeugung in einer Platte bei Kühlung durch Konvektion und Abstrahlung

Zusammenfassung Zur Ermittlung der instationären Temperaturverteilung in einer Platte mit gleichförmiger Wärmeerzeugung wird ein Differenzverfahren vierter Ordnung nach Runge-Kutta angewendet. Die ebene Platte ist einseitig isoliert und wird auf der anderen Seite durch Konvektion und Abstrahlung gekühlt. Zu Beginn befindet sich die Platte gleichförmig auf einer bestimmten Anfangstemperatur, die Temperaturen der umgebenden Objekte sowie des Fluids sind ebenfalls konstant. Der Wärmeleitungsvorgang sei eindimensional. Die Ergebnisse sind in dimensionsloser Form für einen weiten Parameterbereich in Diagrammform dargestellt.

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Nomenclature Bi Biot number - c specific heat - h heat transfer coefficient - k thermal conductivity - L half thickness of plate - Nr Radiation number - T absolute temperature - t time - F _o dimensionless time - T _e environment temperature - T _f fluid temperature - T _i initial plate temperature - u internal energy generation number - u internal energy generation - x space coordinate - x* dimensionless space coordinate Greek symbols thermal diffusivity - emissivity - dimensionless temperature - density - Stephan-Boltzman constant     

The synthesis and structural characterization of transition metal coordination complexes of coumarilic acid

The coumarilate (coum^?) complexes of Co^II(1), Ni^II(2) Cu^II(3) and Zn^II(4) were synthesized and characterized by elemental analysis, magnetic susceptibility, solid-state UV–Vis, FTIR spectra, thermoanalytical TG–DTG/DTA and single-crystal X-ray diffraction methods. It was found that all of the complex structures have 2 mol (coum^?) ligand bonded as monoanionic monodentate in the structures of 1 and 2 while they were coordinated to metal cations as monoanionic bidentate in the complexes 3 and 4. There was not any hydrate water in the metal complexes. The complexes of 1 and 2 have four moles of aqua ligand, and the other complexes have two moles. Thermal decomposition of each complex starts with dehydration, and then the decomposition of organic parts goes. The thermal dehydration of the complexes takes place in one (for the compounds of 2, 3, 4) or two (for the compound 1) steps. The decomposition mechanism and the thermal stability of the complexes under investigation were determined on the basis of their structures. Metal oxides were obtained as the final decomposition product.     

Interactions of halichondrin B and eribulin with tubulin

Compounds that modulate microtubule dynamics include highly effective anticancer drugs, leading to continuing efforts to identify new agents and improve the activity of established ones. Here, we demonstrate that [(3)H]-labeled halichondrin B (HB), a complex, sponge-derived natural product, is bound to and dissociated from tubulin rapidly at one binding site per αβ-heterodimer, with an apparent K(d) of 0.31 μM. We found no HB-induced aggregation of tubulin by high-performance liquid chromatography, even following column equilibration with HB. Binding of [(3)H]HB was competitively inhibited by a newly approved clinical agent, the truncated HB analogue eribulin (apparent K(i), 0.80 μM) and noncompetitively by dolastatin 10 and vincristine (apparent K(i)'s, 0.35 and 5.4 μM, respectively). Our earlier studies demonstrated that HB inhibits nucleotide exchange on β-tubulin, and this, together with the results presented here, indicated the HB site is located on β-tubulin. Using molecular dynamics simulations, we determined complementary conformations of HB and β-tubulin that delineated in atomic detail binding interactions of HB with only β-tubulin, with no involvement of the α-subunit in the binding interaction. Moreover, the HB model served as a template for an eribulin binding model that furthered our understanding of the properties of eribulin as a drug. Overall, these results established a mechanistic basis for the antimitotic activity of the halichondrin class of compounds.