Efficient packing Fourier-transform approach for ultrahigh resolution isotopic distribution calculations.

Fine isotopic structure patterns resolvable by ultrahigh-resolution mass spectrometers are diagnostic of the elemental composition of moderately large compounds. Despite the proven performance of Fourier transforms algorithms to calculate accurate high resolution isotopic distribution, its application to finer ultrahigh resolving power exhibits limited performance. Fast Fourier transforms algorithm requires sampling the relevant range at equally spaced mass values, but ultrahigh resolution mass spectrum displays highly localized complex patterns (peaks) separated in between by relatively large unstructured intervals. Computational efforts consumed on those uninformative intervals are a waste of resources. A fast and memory efficient procedure is introduced in this paper to calculate the isotopic distribution of a single relatively high-mass molecule at ultrahigh resolution by Fourier transforms approaches. The whole isotopic distribution is packed closer to the monoisotopic peak without distorting the actual scale of the peak fine structure. This packing procedure reduced 8 to 32 times the computation resources in comparison to the same calculation performed without packing. The procedure can be readily implemented in existing software.