Detection of minute chemical species by principal-component analysis

A novel analytical technique based on the detection of minute bands in a mixture spectrum with the use of principal-component analysis (PCA) is presented. This new aspect of PCA indicates that overlapped spectra of some components can be separated with no a priori knowledge of the components when the absorbances of the components vary greatly. This technique can be used for the detection of minute chemical species. The concept was confirmed by computer simulations. In the simulations, abstract spectra (loading vectors) were successfully obtained, and the changes of the component absorbances were also successfully followed semiquantitatively by calculating their scores. The method developed with PCA was applied to the analysis of infrared reflection-absorption (RA) spectra to study molecular interaction mechanism between alkyl-deuterated dipalmitoylphosphatidylcholine (DPPC-d(62)) monolayer and sucrose. The samples were Langmuir-Blodgett (LB) films of the DPPC-d(62) monolayer that was prepared on a sucrose solution. The LB films consisted of the following phases:  air/DPPC-d(62) + sucrose/sucrose/substrate (gold). The abstract spectra corresponding to "DPPC-d(62) + sucrose" and "sucrose" phases were successfully separated by PCA, and the absorbance change of sucrose in each phase was semiquantitatively calculated from the score. The absorbance change was experimentally confirmed with quartz-crystal microbalance (QCM) experiments. In addition, minute water molecules that remained in the LB films after drying were readily detected from an abstract spectrum, and their binding site was found to be the phospholipid moiety in the head group of DPPC-d(62).