Advantages of soft versus hard constraints in self-modeling curve resolution problems. Alternating least squares with penalty functions.

A new algorithm for self-modeling curve resolution (SMCR) that yields improved results by incorporating soft constraints is described. The method uses least squares penalty functions to implement constraints in an alternating least squares algorithm, including nonnegativity, unimodality, equality, and closure constraints. By using least squares penalty functions, soft constraints are formulated rather than hard constraints. Significant benefits are (obtained using soft constraints, especially in the form of fewer distortions due to noise in resolved profiles. Soft equality constraints can also be used to introduce incomplete or partial reference information into SMCR solutions. Four different examples demonstrating application of the new method are presented, including resolution of overlapped HPLC-DAD peaks, flow injection analysis data, and batch reaction data measured by UV/visible and near-infrared spectroscopy (NIR). Each example was selected to show one aspect of the significant advantages of soft constraints over traditionally used hard constraints. Incomplete or partial reference information into self-modeling curve resolution models is described. The method offers a substantial improvement in the ability to resolve time-dependent concentration profiles from mixture spectra recorded as a function of time.