A new detection scheme for ultrafast 2D J-resolved spectroscopy

Recent ultrafast techniques enable 2D NMR spectra to be obtained in a single scan. A modification of the detection scheme involved in this technique is proposed, permitting the achievement of 2D 1H J-resolved spectra in 500 ms. The detection gradient echoes are substituted by spin echoes to obtain spectra where the coupling constants are encoded along the direct nu2 domain. The use of this new J-resolved detection block after continuous phase-encoding excitation schemes is discussed in terms of resolution and sensitivity. J-resolved spectra obtained on cinnamic acid and 3-ethyl bromopropionate are presented, revealing the expected 2D J-patterns with coupling constants as small as 2 Hz.     

Adsorption of hydrocarbons on organo-clays--implications for oil spill remediation

Organo-clays synthesised by the ion exchange of sodium in Wyoming Na-montmorillonite (SWy-2-MMT) with three surfactants: (a) octadecyltrimethylammonium bromide (ODTMA), formula C(21)H(46)NBr; (b) dodecyldimethylammonium bromide (DDDMA), formula C(22)H(48)BrN; and (c) di(hydrogenated tallow)dimethylammonium chloride were tested for hydrocarbon adsorption. Using diesel, hydraulic oil, and engine oil an evaluation was made of the effectiveness of the sorbent materials for a range of hydrocarbon products that are likely to be involved in land-based oil spills. It was found that the hydrocarbon sorption capacity of the organo-clays depended upon the materials and surfactants used in the organo-clay synthesis. Greater adsorption was obtained if the surfactant contained two or more hydrocarbon long chains. Extensive utilisation of chemometrics principally with the aid of MCDM methods, produced models which consistently ranked the organo-clays well above any of the competitors including commercial benchmark materials. Thus, the use of organo-clays for cleaning up oil spills is feasible due to its many desirable properties such as high hydrocarbon sorption and retention capacities, hydrophobicity. The negative effects of the use of organo-clays for oil-spill cleanup are the cost, the biodegradability, and recyclability of the organo-clays.     

Sulfonyl vs. carbonyl group: which is the more electron-withdrawing?

Unexpectedly high reactivity of nitrogenated aromatics protected as amides or carbamates, when compared to sulfonamides, can be explained by a decrease of the aromaticity due to a greater ability of the carbon-centered groups to achieve delocalisation of the nitrogen lone pair, resulting in stronger global withdrawing effects.     

A general strategy for ligation of organic and biological molecules to Dawson and Keggin polyoxotungstates

The copper-catalyzed azide/alkyne cycloaddition (click chemistry) is used for the first time in polyoxometalate chemistry to graft any kind of organics (lipophilic, water-soluble, biologically relevant) to polyoxotungstates to generate hybrids. The method is not limited by solvent matching between the polyoxometallic platforms and the organic substrates.     

Increased Lewis acidity in hafnium-substituted polyoxotungstates

Monolacunary polyoxotungstates [alpha(1)-P(2)W(17)O(61)](10-) and [alpha-PW(11)O(39)](7-) react with HfCl(4) to yield [alpha(1)-HfP(2)W(17)O(61)](6-) and [alpha-Hf(OH)PW(11)O(39)](4-), isolated as organo-soluble tetrabutylammonium (TBA) salts. Subsequent analyses, including mass spectrometry, show that they are stronger Lewis acids than (TBA)(5)H(2)[alpha(1)-YbP(2)W(17)O(61)]. The new polyoxotungstates catalyze Lewis acid mediated organic reactions, such as Mukaiyama aldol and Mannich-type additions. In particular, reactions with aldehydes, which were impossible with lanthanide polyoxotungstates, are made possible. Thus these modifications of the polyoxometalate composition allowed fine tuning of the Lewis acidity. The catalysts could be easily recovered and reused.     

Ritz and harmonic Ritz values and the convergence of FOM and GMRES

The Ritz and harmonic Ritz values are approximate eigenvalues, which can be computed cheaply within the FOM and GMRES Krylov subspace iterative methods for solving non‐symmetric linear systems. They are also the zeros of the residual polynomials of FOM and GMRES, respectively. In this paper we show that the Walker–Zhou interpretation of GMRES enables us to formulate the relation between the harmonic Ritz values and GMRES in the same way as the relation between the Ritz values and FOM. We present an upper bound for the norm of the difference between the matrices from which the Ritz and harmonic Ritz values are computed. The differences between the Ritz and harmonic Ritz values enable us to describe the breakdown of FOM and stagnation of GMRES. Copyright © 1999 John Wiley & Sons, Ltd.     

Relationship between the lower frequency spectrum of plates and networks of beams

We give the behaviour of the lower frequency spectrum of a sequence of networks of beams which cover a given plate with a smooth boundary. This behaviour is obtained by means of a finite difference scheme of the membrane. Copyright © 2000 John Wiley & Sons, Ltd.     

Weinberg bounds over nonspherical graphs

Let Aut(G) and E(G) denote the automorphism group and the edge set of a graph G, respectively. Weinberg's Theorem states that 4 is a constant sharp upper bound on the ratio |Aut(G)|/|E(G)| over planar (or spherical) 3‐connected graphs G. We have obtained various analogues of this theorem for nonspherical graphs, introducing two Weinberg‐type bounds for an arbitrary closed surface Σ, namely: where supremum is taken over the polyhedral graphs G with respect to Σ for W_P(Σ) and over the graphs G triangulating Σ for W_T(Σ). We have proved that Weinberg bounds are finite for any surface; in particular: W_P = W_T = 48 for the projective plane, and W_T = 240 for the torus. We have also proved that the original Weinberg bound of 4 holds over the graphs G triangulating the projective plane with at least 8 vertices and, in general, for the graphs of sufficiently large order triangulating a fixed closed surface Σ. © 2000 John Wiley & Sons, Inc. J Graph Theory 33: 220–236, 2000