Interpretation of static time-of-flight secondary ion mass spectra of adsorbed protein films by multivariate pattern recognition.

Multivariate analysis has become increasingly common in the analysis of multidimensional spectral data. We previously showed that the multivariate analysis technique principal component analysis (PCA) is an excellent method for interpreting the static time-of-flight secondary ion mass spectrometry (TOF-SIMS) spectra of adsorbed protein films. PCA is an unsupervised pattern recognition technique that loses resolution between spectra of different proteins as more proteins are added to the data set due to large within-group variation. The supervised pattern recognition techniques discriminant principal component analysis (DPCA) and linear discriminant analysis (LDA), which aim to control within-group variation while maximizing between-group separation to enhance discrimination between groups, were compared with PCA using data sets of TOF-SIMS spectra of proteins adsorbed onto mica and PTFE substrates. DPCA and LDA quantitatively improved discrimination between groups and provided different information about the data than PCA. LDA was able to classify unknown samples with a misclassification rate lower than PCA or DPCA. Both unsupervised and supervised pattern recognition techniques are useful for the interpretation and classification of static TOF-SIMS spectra of adsorbed protein films.