A new approach to data reduction and evaluation in high-resolution time-of-flight mass spectrometry using a...

A new effective and robust approach to the detection of incompletely resolved peaks, and evaluation of their parameters in high-resolution time-of-flight mass spectra for time-to-digital convertor (TDC) data acquisition mode, is described. The method is based on fast construction of a smoothed continuous curve that approximates the initial data (transformed to a constant relative width of time intervals for ion counting) with respect to precision of measurements. The first derivative of this curve is used for correction of skewness of the peak shape as far as possible. A contribution of the second derivative is subtracted from the smoothed curve for better resolution of partially resolved peaks. The comparison of local maxima of this resulting final curve with those for the initial smoothed curve allows reliable detection of the peaks and to test whether or not they are spoiled by overlapping. Ion counting performed by TDC gives an opportunity to estimate standard deviations of peak locations and their intensities. These values proved to be close to theoretically minimal standard deviations for these parameters for single fully resolved peaks. Thus, estimates of the main parameters of mass peaks by the described method are close to statistically efficient estimators for these parameters.