The effect of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry instrumentation parameters on the matrix-assisted laser desorption/ionization simulated size exclusion chromatography number-mass, average-weight and polydispersity values of dextran against corresponding values obtained by size exclusion chromatography.

The matrix-assisted laser desorption/ionization simulated size exclusion chromatography (SECPC) average-number mass, weight average and polydispersity of dextran 1000 were determined by matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometry. The instrument parameters were varied and the SECPC value determined via the Bruker XMASS software was compared to the value obtained from aqueous-phase size exclusion chromatography. The aqueous-phase size exclusion chromatography values for average-number mass, weight average and polydispersity were 1223 Da, 1500 Da and 1.23 (1010 Da, 1270 Da and 1.26 from manufacturer), whereas the SECPC value varied on the instrumental parameters. The factors that had the greatest effect on the average-number mass, weight average and polydispersity were: (most effect on SECPC value) laser attenuation > matrix-analyte molar concentration > matrix-analyte molar ratios > delay extraction time > solvent-system composition > detector delay (least effect on SECPC value). The oligosaccharide signal distribution as a function of laser attenuation indicate that two distinct regions exist in dextran 1000, where one corresponds to the higher mass oligosaccharides (hexasaccharide or greater), while another region corresponds to lower oligosaccharides (tetra-saccharide). This distribution depends upon the crystallization of the biopolymer and the efficiency of desorption/ionization, which yields the SECPC value. There was broad agreement between the SECPC values and size exclusion chromatography values for dextran, although the polydispersity indicated by SECPC was less than size exclusion chromatography (1.10 vs. 1.26). It can be shown that for narrow polydisperse biopolymers the instrumental conditions are less critical in the determination of average-number mass, weight average and polydispersity, although the SECPC Mn, and weight average values are often higher than the corresponding values obtained by aqueous-phase size exclusion chromatography.

The Ion Conveyor. An ion focusing and conveying device.

The control and transmission of ions or small charged droplets in the intermediate to high-pressure regime is of primary importance in areas such as atmospheric pressure ionisation. Where small apertures separate differentially pumped vacuum regions in the inlet systems to mass spectrometers, a large proportion of the available ion current is lost to the surrounding electrode structures. A new ion-optical device, named the ion conveyor, incorporating electrodynamic focusing and conveying of charged entities is described. Results from ion-optical simulations are presented demonstrating the performance of the device in various operating modes and electrode configurations.

Determination of end groups of synthetic polymers by matrix-assisted laser desorption/ionization: high-energy collision-induced dissociation.

Matrix-assisted laser desorption/ionization has been combined with high-energy collision-induced dissociation for the analysis of poly(ethylene glycols) with butanoyl, benzoyl and acetyl end groups, using novel technology comprising a magnetic-sector mass spectrometer and ion buncher with an in-line quadratic-field ion mirror. High-energy (>8 keV) collision-induced dissociation facilitated unambiguous end-group determination of these polymers, providing masses of end groups and structural information. The high-energy collision-induced dissociation also provided information regarding repeat units.