Accelerated isotope fine structure calculation using pruned transition trees.

A fast and memory-efficient calculation of theoretical isotope patterns is crucial for the routine interpretation of mass spectrometric data. For high-resolution experiments, calculations must procure the exact masses and probabilities of relevant isotopologues over a wide range of polyisotopic compounds, while pruning low-probable ones. Here, a novel albeit simple treelike structure is introduced to swiftly derive sets of relevant subisotopologues for each element in a molecule, which are then combined to the isotopologues of the full molecule. In contrast to existing approaches, transitions via single replacements of the most abundant isotope per element are used in separable tree branches to derive subisotopologues from each other. Moreover, the underlying transition trees prevent redundant replacements and permit the detection of the most probable isotopologue in a first phase. A relative threshold can then be exploited in a second parallelized phase for a precise prepruning of large fractions of the remaining subisotopologues. The gain in performance from such early pruning and the lower variation in the distortion of simulated data with use of relative rather than absolute thresholds were validated in a large-scale benchmark simulation, unprecedentedly comprising several thousand molecular formulas. Both the algorithm and a wealth of related features are freely available as R-package enviPat and as a user-friendly Web interface.