Numerical optimization of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry: application to synthetic polymer molecular mass distribution measurement.

A novel approach is described for the selection of optimal instrument parameters that yield a mass spectrum which best replicates the molecular mass distribution of a synthetic polymer. The application of implicit filtering algorithms is shown to be a viable method to find the best instrument settings while simultaneously minimizing the total number of experiments that need to be performed. This includes considerations of when to halt the iterative optimization process at a point when statistically-significant gains can no longer be expected. An algorithm to determine the confidence intervals for each parameter is also given. Details on sample preparation and data analysis that ensure stability of the measurement over the time scale of the optimization experiments are provided. This work represents part of an effort to develop an absolute molecular mass distribution polymer Standard Reference Material.