Generalization of the lineshape useful in magnetic resonance spectroscopy

A new lineshape function is derived from the Tsallis distribution to describe electron paramagnetic resonance (EPR) spectra, and possibly nuclear magnetic resonance (NMR) spectra as well. This lineshape generalizes the Gaussian and Lorentzian lineshapes that are widely used in simulations. The main features of this lineshape function are presented: the normalization, moments, and first derivative. A number of experimental EPR spectra are compared with the results of simulations employing the new lineshape function. The results show that the new lineshape often provides a better approximation of the experimental spectrum. It is also shown that the new parameter of the lineshape function can be used to quantify the intermolecular spin-spin interactions.     

Addition of dipropylamine to multiacrylate and its model compound catalyzed by lithium dipropylamide

The nucleophilic addition reaction of dipropylamine to vinyl groups of multiacrylate - poly(2-acryloyloxyethyl methacrylate) and to 2-butyrylethyl acrylate as model compound has been investigated. Based on the results obtained, it has been shown that the addition reaction rate of dipropylamine to multiacrylate and 2-butyrylethyl acrylate is proportional to [CH₂=CH-] and to [(C₃H₇)₂NLi] with the ratio [(C₃H₇)₂NH]_o/[(C₃H₇)₂NLi]_o = 20. Second-order addition reaction rate constants and activation energies for the systems under investigation have been determined. This revised version was published online in August 2006 with corrections to the Cover Date.     

From 1/f noise to multifractal cascades in heartbeat dynamics

We explore the degree to which concepts developed in statistical physics can be usefully applied to physiological signals. We illustrate the problems related to physiologic signal analysis with representative examples of human heartbeat dynamics under healthy and pathologic conditions. We first review recent progress based on two analysis methods, power spectrum and detrended fluctuation analysis, used to quantify long-range power-law correlations in noisy heartbeat fluctuations. The finding of power-law correlations indicates presence of scale-invariant, fractal structures in the human heartbeat. These fractal structures are represented by self-affine cascades of beat-to-beat fluctuations revealed by wavelet decomposition at different time scales. We then describe very recent work that quantifies multifractal features in these cascades, and the discovery that the multifractal structure of healthy dynamics is lost with congestive heart failure. The analytic tools we discuss may be used on a wide range of physiologic signals. (c) 2001 American Institute of Physics.     

Experimental and computational study on the reactivity of 2,3-bis[(3-pyridylmethyl)amino]-2(Z)-butene-1,4-dinitrile, a key intermediate for the synthesis of tribenzoporphyrazine bearing peripheral methyl(3-pyridylmethyl)amino substituents

Abstract  

An earlier developed alkylating path leading to tetraalkylated diaminomaleonitrile derivatives was explored. Attempts to explain the reactivity of the representative dialkylated diaminomaleonitrile 2,3-bis[(3-pyridylmethyl)amino]-2(Z)-butene-1,4-dinitrile during the alkylation reaction were performed using X-ray and density functional theory (DFT) studies. The condensed Fukui functions accompanied by softness indices were found to be useful in explaining its reactivity observed during the reaction. The values of the Fukui functions and condensed softness for electrophilic attack calculated from Mulliken, L?wdin, and natural population analyses closely corresponded to the experimental observations. When 2,3-bis[(3-pyridylmethyl)amino]-2(Z)-butene-1,4-dinitrile disodium salt was treated with dimethyl sulfate at lower temperatures the alkylation reaction prevailed, whereas at higher temperatures the alkylating agent acted as a hydride anion acceptor, which favored the elimination reaction. The tetraalkylated dinitrile 2,3-bis[methyl(3-pyridylmethyl)amino]-2(Z)-butene-1,4-dinitrile was used in the synthesis of tribenzoporphyrazine bearing methyl(3-pyridylmethyl)amino groups, which was subsequently subjected to solvatochromic and metallation studies. The changes observed during metallation seem to result from the coordination of the 3-pyridyl group by a palladium ion. This could influence the configuration of the methyl(3-pyridylmethyl)amino moiety, causing more effective donation of a lone pair of electrons from peripheral nitrogen to the macrocyclic ring.     

Activity changes of glassy carbon electrodes caused by their exposure to OH• radicals

GC electrodes were exposed to Fenton solutions. The surface changes produced by the OH^? radicals of these solution were inspected using SEM, XPS, Raman spectroscopy and electrochemistry. The OH^? radicals caused erosion and roughening of the surface, selective oxidation and dissolution of sp² carbon, and reduction of the number of nucleation sites for silver deposition.     

On uniform estimate in Calabi-Yau theorem

We show that the uniform estimate in the Calabi-Yau theorem easily follows from the local stability of the complex Monge-Ampère equation.

     

Synthesis of betulin derivatives and the determination of their relative lipophilicities using reversed‐phase thin‐layer chromatography

A series of superlipophilic or highly lipophilic semisynthetic betulin derivatives was prepared and their relative lipophilicity was measured by reversed‐phase thin‐layer chromatography (RP‐TLC) at different pH values using 1,4‐dioxane–acetate buffer mixtures as mobile phases. Cholesterol, 17β‐estradiol and pure betulin were used as the reference compounds. Linear relationships were found between R_M values and 1,4‐dioxane concentrations in the mobile phases. LogP values were also calculated with computer programs ACD/LogP (ChemSketch 11.0, Advanced Chemistry Development Inc.) and ClogP (Daylight Chemical Information Systems Inc.). The empirical and theoretical data were compared, and the R_M0 values correlated well with logP. Two of the synthesized betulin derivatives are reported for the first time. Copyright © 2009 John Wiley & Sons, Ltd.