Silver cluster interferences in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry of nonpolar polymers

Potential difficulties associated with background silver salt clusters during matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) of nonpolar polymers are reported. Silver salt cluster ions were observed from m/z 1500 to 7000 when acidic, polar matrices, such as 2,5-dihydroxybenzoic acid (DHB), all-trans-retinoic acid (RTA) or 2-(4-hydroxyphenylazo)benzoic acid (HABA), were used for the analysis of nonpolar polymers. These background signals could be greatly reduced or eliminated by the use of nonpolar matrices such as anthracene or pyrene. Representative examples of these background interferences are demonstrated during the analysis of low molecular weight nonpolar polymers including polybutadiene and polystyrene. Nonpolar polymers analyzed with acidic, polar matrices (e.g., RTA) and silver cationization reagents can yield lower quality mass spectral results when interferences due to silver clusters are present. Replacing the polar matrices with nonpolar matrices or the silver salts with copper salts substantially improved the quality of the analytical results. In addition, it was found that silver contamination cannot be completely removed from standard stainless steel sample plates, although the presence of silver contamination was greatly reduced after thorough cleaning of the sample plate with aluminum oxide grit. Carry-over silver may cationize polymer samples and complicate the interpretation of data obtained using nonpolar matrices in the absence of added cationization reagents.     

Evidence for a solid phase of dodecahedral C 20

Evidence is presented for the formation of a solid phase based on the smallest fullerene, C₂₀, in thin diamond-like carbon films deposited by ultraviolet laser ablation from diamond onto nickel substrates at room temperature in the presence of 10^-4 torr of cyclohexane or benzene. Laser desorption mass spectrometry from the films shows the presence of C₂₀, C₂₁ and C₂₂ species, while micro-Raman spectroscopy and electron diffraction from selected particles together with first principle density-functional calculations, indicate a cubic solid with dodecahedral C₂₀ cages as building blocks. Unlike solid C₆₀ and fully protonated C₂₀, which are bound by van der Waals forces, the proposed structure is stabilized by linking of the C₂₀ dodecahedra with bridging carbon atoms at interstitial tetrahedral sites to form a face-centered-cubic lattice with 22 carbon atoms per unit cell. Received 10 October 2002 / Received in final form 24 December 2002 Published online 6 March 2003 RID="a" ID="a"e-mail: zafar.iqbal@njit.edu     

Tuning the electronic and magnetic properties of boron nitride nanotubes

Density Functional Theory is used to investigate the effect of altering the B/N ratio and carbon doping on the electronic and magnetic structure of zigzag, (7, 0) and armchair (5, 5) boron nitride nanotubes. The calculations indicate that increasing the boron content relative to the nitrogen content significantly reduces the band gap to a value typical of a semiconductor. Calculations of carbon doped semiconducting BN tubes, which have more boron atoms than nitrogen atoms have a net spin and a difference in the density of states at the valence band between the spin up and spin down state.     

An algorithm for constrained convex optimization

This paper presents a feasible direction algorithm for the minimization of a pseudoconvex function over a smooth, compact, convex set. We establish that each cluster point of the generated sequence is an optimal solution of the problem without introducing anti-jamming procedures. Each iteration of the algorithm involves as subproblems only one line search for a zero of a continuously differentiable convex function and one univariate function minimization on a compact interval.     

A new microstructure-based constitutive model for human blood

A new constitutive equation for whole human blood is derived using ideas drawn from temporary polymer network theory to model the aggregation and disaggregation of erythrocytes in normal human blood at different shear rates. Each erythrocyte is represented by a dumbbell. The use of a linear spring law in the dumbbells leads to a multi-mode generalized Maxwell equation for the elastic stress and both the relaxation times and viscosities are functions of a time-dependent structure variable. An approximate constitutive equation is derived by choosing a single mode corresponding to the cell aggregate size where the largest number of cells are to be found. This size is identified in the case of steady flows. The model exhibits shear-thinning, viscoelasticity and thixotropy and these are clearly related to the microstructural properties of the fluid. Agreement with the experimental data of Bureau et al. [M. Bureau, J.C. Healy, D. Bourgoin, M. Joly, Rheological hysteresis of blood at low shear rate, Biorheology 17 (1980) 191–203] in the case of a simple triangular step shear rate flow is convincing.     

The use of a high-modulus-inclusion gage in nonlinear viscoelastic materials

The behavior of an inclusion in a host material subjected to a stress system depends primarily on the ratio of the tangent moduli,E inclusion/E host. An inclusion of suitable material used in the form of a gage will give an identifiable photoelastic-fringe pattern. This pattern is related to the applied biaxial stresses in the diametral plane of the gage, and is independent of the actual modulus and strains in the host material provided that the moduli ratio is more than 300. A program of work has been carried out to verify the use of such an inclusion gage in low-modulus nonlinear viscoelastic materials. The gage geometry used in this work consisted of a hollow cylinder of birefringent material with a ratio of outside diameter to inside diameter of 5 to 1. The host materials were either unfilled or highly filled carboxyl-terminated polybutadiene rubbers. The moduli ratios for both host materials were such that the gages act as rigid inclusions. A theoretical study has also been conducted to find the optimum measuring points within the gage and the fringe patterns created by selected biaxial-stress ratios. The study also showed that the gage sensitivity is virtually independent of Poisson's ratio but depends on the biaxial ratio of the stresses. The values of the sensitivity factor obtained experimentally were close to those derived theoretically. The stressfringe order at the optimum measuring points was obtained by Tardy compensation, and the biaxial-stress ratio determined either from fringe-pattern recognition or by measuring points. Future applications and uses of such a stress-measuring technique will be described.