Determining a 'safe' high-mass limit in matrix-assisted laser desorption/ionisation time-of-flight mass spectra of coal derived materials with reference to instrument noise

Three methods for determining a 'safe' estimate for high-mass limits of MALDI spectra of coal derived liquids were explored, using a sample of coal-tar pitch and its pyridine-insoluble fraction. Co-addition of increasing numbers of single-shot spectra (10, 30, 50 and 100 pulses) showed visually observable reductions in noise levels, consistent with robust and statistically meaningful signals. Three separate types of post-acquisition calculation were used to identify high-mass limits of the spectra. (i) A literature method indicated high-mass limits similar to those observed visually-as a shift from baseline at the highest masses, nearly 350 000 u for the coal tar pitch and about 390 000 u for its pyridine insoluble fraction. (ii) Comparing instrument signal with pre-selected multiples of the standard deviation, upper mass estimates of between 40-60 000 u for the coal-tar pitch and about 95 000 u for its pyridine-insoluble fraction were found. (iii) Calculation of the slope was used to identify 'lift-off' of the spectrum from baseline. The angle between the smoothed spectrum and the baseline was matched to a pre-selected value (e.g. 0.5 degrees and 1 degrees ). However, the arbitrary specification of the key parameter did not establish this last method on a firm basis. The choice of a criterion for estimating high-mass limits of MALDI spectra remains a semi-quantitative procedure; a reasonably conservative high-mass limit may be estimated by comparison of signal with five times the standard deviation. However, evaluation of size exclusion chromatograms of the present samples using polystyrene standards suggests that molecular mass distributions of pitch samples arrived at by MALDI mass spectrometry are, at least partly, determined by the limitations of available instruments. Copyright 1999 John Wiley & Sons, Ltd.     

Generalized filters, the low-pass condition, and connections to multiresolution analyses

We study generalized filters that are associated to multiplicity functions and homomorphisms of the dual of an abelian group. These notions are based on the structure of generalized multiresolution analyses. We investigate when the Ruelle operator corresponding to such a filter is a pure isometry, and then use that characterization to study the problem of when a collection of closed subspaces, which satisfies all the conditions of a GMRA except the trivial intersection condition, must in fact have a trivial intersection. In this context, we obtain a generalization of a theorem of Bownik and Rzeszotnik.     

A direct integral decomposition of the wavelet representation

In this paper we use the concept of wavelet sets, as introduced by X. Dai and D. Larson, to decompose the wavelet representation of the discrete group associated to an arbitrary integer dilation matrix as a direct integral of irreducible monomial representations. In so doing we generalize a result of F. Martin and A. Valette in which they show that the wavelet representation is weakly equivalent to the regular representation for the Baumslag-Solitar groups.

     

A magic-angle rotor for NMR using a forced gas bearing

A new design for a rotor system to achieve spinning rates of the order of 3 kHz is presented. The design uses a simple cylindrical rotor, and involves a forced air bearing over the whole cylindrical surface. The jets of gas which make this bearing also cause the spinning. Powder-filled hollow rotors spin smoothly, and are convenient to make and use. The whole system is suitable for magic angle rotation, such as is needed to obtain high-resolution NMR spectra of solids. Examples of spectra obtained using the device are illustrated and discussed.     

NMR relaxation and pulsed field gradient study of alginate bead porous media

Experiments are presented, which correlate molecular displacement with the multi-exponential T2 relaxation times of water flowing and diffusing through an alginate bead pack. Three systems were studied comprising beads of 3, 1 or < mm in diameter. T2-resolved propagators were obtained through a combined pulsed gradient stimulated echo (PGSTE) and Carr-Purcell-Meiboom-Gill (CPMG) experiment. Fourier transformation with respect to q produces a propagator for each echo in the CPMG train. Inverse Laplace transformation of the CPMG decays for each point (Z) in the propagator produced a two-dimensional propagator. Analysis of these two-dimensional propagators provided insight into the transport and exchange behaviour of water flowing through this system. This experiment has been simulated in a model bead structure and the resulting T2 relaxation time behaviour and T2-resolved propagators were found to be in good agreement with the experimental data. We also present a theoretical analysis of the response to the combined PGSTE/CPMG sequence in the simple model case of Pouseille flow in a cylindrical capillary, where diffusion to a surface sink is assumed to be the dominant relaxation mechanism.