Applied Mathematics Commons^™

Properly Handling Negative Values In The Calculation Of Binding Constants By Physicochemical Modeling Of Spectroscopic Titration Data, Nathanael P. Kazmierczak, Douglas A. Vander Griend

University Faculty Publications and Creative Works

To implement equilibrium hard-modeling of spectroscopic titration data, the analyst must make a variety of crucial data processing choices that address negative absorbance and molar absorptivity values. The efficacy of three such methodological options is evaluated via high-throughput Monte Carlo simulations, root-mean-square error surface mapping, and two mathematical theorems. Accuracy of the calculated binding constant values constitutes the key figure of merit used to compare different data analysis approaches. First, using singular value decomposition to filter the raw absorbance data prior to modeling often reduces the number of negative values involved but has little effect on the calculated binding constant …