Solvent effects on substitution reactions at complexes of the [Fe(CN)5L]3- type in binary aqueous mixtures

Summary The kinetics of replacement of 4,4-bipyridine, (4,4-bipy), and 4-cyanopyridine, (4-CNpy), by cyanide in [Fe(CN)₅-(4,4-bipy)]^3-. at 298 K have been studied in binary aqueous mixtures containing different amounts of t-butanol, methanol, glycerol, ethyleneglycol and sucrose. The plots of logarithms of the limiting rate constantsversus the mole fraction of water are linear over the entire composition range studied, showing the importance of solvation phenomena. A different straight line of log (k_L/s^–1)versus X_H2O is obtained for each mixture, indicating the influence of other solvent parameters on the reaction rate. A multiparameter regression of G _exp with A (acidity vector), B (basicity vector) and G^E is used for both reactions; plots of G _calc versus G _exp are linear with slopes of near unity.     

Braided Logic: The Simplest Models

The only pair of binary classical essential connectives for which the Artin braid relation holds is a distributive lattice, i.e. the Boolean disjunction and conjunction of     

Complete 1H NMR assignments of pyrrolizidine alkaloids and a new eudesmanoid from Senecio polypodioides

Chemical investigation of the aerial parts of Senecio polypodioides lead to the isolation of the new eudesmanoid 1β‐angeloyloxyeudesm‐7‐ene‐4β,9α‐diol ( 1 ) and the known dirhamnosyl flavonoid lespidin ( 3 ), while from roots, the known 7β‐angeloyloxy‐1‐methylene‐8α‐pyrrolizidine ( 5 ) and sarracine N‐oxide ( 6 ), as well as the new neosarracine N‐oxide ( 8 ), were obtained. The structure of 1 and 8 was elucidated by spectral means. Complete assignments of the ¹H NMR data for 5 , 6 , sarracine ( 7 ), and 8 were made using one‐dimensional and two‐dimensional NMR experiments and by application of the iterative full spin analysis of the PERCH NMR software. Copyright © 2014 John Wiley & Sons, Ltd.     

Multi-scale RoIs selection for classifying multi-spectral images

Multidimensional Systems and Signal Processing - The applications of object-based image analysis (OBIA) in remote sensing studies have received a considerable amount of attention over the recent...     

Joint spectrum and power optimization in the design of the UMTS satellite component

The paper provides a power and spectrum joint analysis of the universal mobile telecommunications system (UMTS) satellite component, based on the wideband code division multiple access (W‐CDMA) air interface. In fact, power and spectral efficiency may become highly conflicting requirements in a satellite system and a trade‐off analysis is needed to drive a proper dimensioning of the satellite. The proposed approach allows a dimensioning of the satellite component either in terms of orbit and power budget or in terms of additional capacity for the terrestrial section, for specified orbit and power limitations. The impact of candidate frequency bands, orbit type and diversity on both spectral and power requirements of the satellite component is evaluated. For given traffic requirements, power‐vs‐spectrum trade‐off is proposed which ensures a proper resources utilization. The efficiency evaluation accounts for: beams overlapping, ortho gonality, voice activity factor, diversity and cross‐polarization frequency reuse. Perfect power control is assumed and the effect of the excess power required by the shadowed users is accounted for in the interference calculation. Furthermore, still in the frame of a proper resource exploitation, a possible optimization of capacity through the use of unpaired bands in the two link directions is analysed. Copyright © 2001 John Wiley & Sons, Ltd.     

Volumes of activation for dissociation of pentacyanoferrates(II) through pressure and salt effects on reactivity

Summary Dependences of rate constants on pressure (up to 1 kbar) and on added salt concentration (up to 6.0 mol dm^–3 LiNO₃, NaNO₃, NaCl, Na₂SO₄ or KNO₃) have been established for dissociative substitution of pentacyanoferrates(II), [Fe(CN)₅L]^3– with L = 4-cyanopyridine, 4,4-bipyridyl, 4-phenylpyridine and 4-t-butylpyridine. Activation volumes derived directly from pressure effects, and indirectly from salt effects via surface tension dependences and derived surfaces of activation, are reported, compared and discussed.