Stupid statistics!
The method of least squares is probably the most powerful data analysis tool available to scientists. Toward a fuller appreciation of that power, this work begins with an elementary review of statistics fundamentals, and then progressively increases in sophistication as the coverage is extended to the theory and practice of linear and nonlinear least squares. The results are illustrated in application to data analysis problems important in the life sciences. The review of fundamentals includes the role of sampling and its connection to probability distributions, the Central Limit Theorem, and the importance of finite variance. Linear least squares are presented using matrix notation, and the significance of the key probability distributions-Gaussian, chi-square, and t-is illustrated with Monte Carlo calculations. The meaning of correlation is discussed, including its role in the propagation of error. When the data themselves are correlated, special methods are needed for the fitting, as they are also when fitting with constraints. Nonlinear fitting gives rise to nonnormal parameter distributions, but the 10% Rule of Thumb suggests that such problems will be insignificant when the parameter is sufficiently well determined. Illustrations include calibration with linear and nonlinear response functions, the dangers inherent in fitting inverted data (e.g., Lineweaver-Burk equation), an analysis of the reliability of the van't Hoff analysis, the problem of correlated data in the Guggenheim method, and the optimization of isothermal titration calorimetry procedures using the variance-covariance matrix for experiment design. The work concludes with illustrations on assessing and presenting results.
Tellinghuisen
Joel
J
Department of Chemistry, Vanderbilt University, Nashville, Tennessee 37235, USA.
D002138:Calibration; D003627:Data Interpretation, Statistical; D016018:Least-Squares Analysis; D009010:Monte Carlo Method; D017711:Nonlinear Dynamics