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The initial steps of the folding pathway of the C-terminal domain of the murine prion protein mPrP(90–231) are predicted based on the sequential collapse model (SCM). A non-local dominant contact is found to form between the connecting region between helix 1 and β-sheet 1 and the C-terminal region of helix 3. This non-local contact nucleates the most populated molten globule-like intermediate along the folding pathway. A less stable early non-local contact between segments 120–124 and 179–183, located in the middle of helix 2, promotes the formation of a less populated molten globule-like intermediate. The formation of the dominant non-local contact constitutes an example of the postulated Nature’s Shortcut to the prion protein collapse into the native structure. The possible role of the less populated molten globule-like intermediate is explored as the potential initiation point for the folding for three pathogenic mutants (T182A, I214V, and Q211P in mouse prion numbering) of the prion protein. 

Abstract The photo-induced dissociative-ionization of lanthanide complexes Ln(hfac)₃(Ln = Pr, Er, Yb) is studied using intense ultrafast transform limited (TL) and linearly chirped laser pulses in a time-of-flight (TOF) mass spectrometry setup. Various fluorine and Ln-containing high-mass fragments were observed in this experiment, including the molecular parent ion, which have not been seen with previous studies relying on relatively long-duration laser pulses (i.e., ns or longer). These new high-mass observations provide important formerly missing information for deducing a set of photo-fragmentation mechanistic pathways for Ln(hfac)₃. An overall ultrafast control mechanism is proposed by combining insights from earlier studies and the fragments observed in this research to result in three main distinct photo-fragmentation processes: (a) ligand-metal charge transfer, (b) CF₃elimination, and (c) C-C bond rotation processes. We conclude that ultrafast dissociative-ionization could be a promising technique for generating high-mass fragments for potential use in material science applications.