Generalized graph entropies

This article deals with generalized entropies for graphs. These entropies result from applying information measures to a graph using various schemes for defining probability distributions over the elements (e.g., vertices) of the graph. We introduce a new class of generalized measures, develop their properties, compute the measures for selected graphs, and briefly discuss potential applications to classification and clustering problems. © 2011 Wiley Periodicals, Inc. Complexity, 17,45–50, 2011     

A classification tree approach for the modeling of competing risks in discrete time

Advances in Data Analysis and Classification - Cause-specific hazard models are a popular tool for the analysis of competing risks data. The classical modeling approach in discrete time consists of...     

Thermodynamics and Spectroscopy of Halogen- and Hydrogen-Bonded Complexes of Haloforms with Aromatic and Aliphatic Amines

Similarities and differences of halogen and hydrogen bonding were explored via UV–Vis and ¹H NMR measurements, X-ray crystallography and computational analysis of the associations of CHX₃ (X=I, Br, Cl) with aromatic (tetramethyl-p-phenylenediamine) and aliphatic (4-diazabicyclo[2,2,2]octane) amines. When the polarization of haloforms was taken into account, the strengths of these complexes followed the same correlation with the electrostatic potentials on the surfaces of the interacting atoms. However, their spectral properties were quite distinct. While the halogen-bonded complexes showed new intense absorption bands in the UV–Vis spectra, the absorptions of their hydrogen-bonded analogues were close to the superposition of the absorption of reactants. Additionally, halogen bonding led to a shift in the NMR signal of haloform protons to lower ppm values compared with the individual haloforms, whereas hydrogen bonding of CHX₃ with aliphatic amines resulted in a shift in the opposite direction. The effects of hydrogen bonding with aromatic amines on the NMR spectra of haloforms were ambivalent. Titration of all CHX₃ with these nucleophiles produced consistent shifts in their protons’ signals to lower ppm values, whereas calculations of these pairs produced multiple hydrogen-bonded minima with similar structures and energies, but opposite directions of the NMR signals’ shifts. Experimental and computational data were used for the evaluation of formation constants of some halogen- and hydrogen-bonded complexes between haloforms and amines co-existing in solutions.     

Tailored Palladium Catalysts for Selective Synthesis of Conjugated Enynes by Monocarbonylation of 1,3‐Diynes

For the first time, the monoalkoxycarbonylation of easily available 1,3‐diynes to give synthetically useful conjugated enynes has been realized. Key to success was the design and utilization of the new ligand 2,2′‐bis(tert‐butyl(pyridin‐2‐yl)phosphanyl)‐1,1′‐binaphthalene (Neolephos), which permits the palladium‐catalyzed selective carbonylation under mild conditions, providing a general preparation of functionalized 1,3‐enynes in good‐to‐high yields with excellent chemoselectivities. Synthetic applications that showcase the possibilities of this novel methodology include an efficient one‐pot synthesis of 4‐aryl‐4H‐pyrans as well as the rapid construction of various heterocyclic, bicyclic, and polycyclic compounds.     

A new mode of activation of CO2 by metal-ligand cooperation with reversible C-C and M-O bond formation at ambient temperature

Team work: Although CO(2) binding to metal centers usually involves π coordination to a C=O group or σ bonds to the carbon or oxygen atom of the CO(2) molecule, a new mode of metal-ligand cooperative activation of CO(2) to a ruthenium PNP pincer complex involving aromatization/dearomatization steps is presented in experimental and theoretical studies (see scheme).     

Kolmogorov scaling of turbulent flow in the vicinity of the wall

How to scale even the simplest of turbulent flows continues to be a cause for considerable controversy. In the present research, a data base compiling results from channel flow direct numerical simulations and turbulent boundary layer experiments is employed to investigate the properties of shear and normal Reynolds stresses very close to the wall. Two types of scaling based on Kolmogorov length and velocity scales are analyzed. It is shown that it is highly likely that large length scales of the order of the channel half-width or the boundary layer thickness play an important role even in the innermost regions of wall-bounded turbulent flows, which hints at the persistence of Reynolds number effects in even high Reynolds number flows.