A new scheme for quantitative analysis of a multicomponent fluorescent mixture using the Excitation-Emission Matrix (EEM) acquired by the video fluorometer has been developed and tested. This method, rank annihilation, Is capable of quantifying a particular component known to be present In the mixture without having also to know the Identity of the rest of the components. The theory of the method and the results of Its application to a mixture matrix are presented and comparison Is made with the method of least squares.

10 min, the levels of contamination reached in the supernates, a s measured by absorbances a t 220 nm, were 0.006, 0.003, 0.003, 0.002, 0.001, and 0.001, respectively (same order as before). By comparison to a value of 0.082 for an unprewashed filter of type I1 shaken with 5 mL of distilled water for 10 min (as shown in Figure l), it is evident that the prewashing was (3) Gillespie, D.; Spiegelman, S. Briggs, R. 0.; Garanchon, C. M.; Ouellet, M. J.; Graf, E. A.; Luckhurst, D. G. J , Parenteral Drug Assoc. 1980, in press.highly effective. LITERATURE CITED(1) Liu. S. T.; Carney, C. F.; Hurwitz, A . R. The usefulness of the method of rank annihilation for quantitative analyses of multicomponent fluorescence data as acquired in the form of an excitation-emission matrix (EEM) by the videofluorometer is exemplified using ten different samples of a six-component polynuclear aromatic hydrocarbonsolution whose constituents have a wide range of fluorescence quantum efficiencies and spectral overlaps. The optimal number of basis vectors to adequately represent the mixture EEMs, the best eigenvalue to minimize, and other criteria for increasing the reliability of the calculated results are explored.

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A technique based on the rapid scanning capability of the video fluorometer to acquire an emission-excitation matrix (EEM) has been developed for phosphorimetry. This technique overcomes the problem of convolution of time decay with phosphorescence excitation and emission spectra by integrating the signal on target. This method also circumvents the need for very rapid acquisition of data for samples with phosphors of very short lifetimes. A phosphorescence emission-excitation matrix (PEEM) obtained in this manner permits time resolution. Sets of each tlme-PEEM allow a ratio deconvolution algorithm to successfully resolve mixtures of polynuclear aromatic compounds.