(a) Arrival time distributions (ms) of +7 charge state of FGF1 (upper), +7 charge state of 1:1 FGF1–HS dp4a complex (middle) and +12 charge state of 2:1 FGF1–HS dp4a complex (lower). The narrow arrival time distribution observed for each species indicates that the native structure of FGF1 and the noncovalent complex of FGF1 with HS are stable in the TWIMS experiment. (b) Arrival time distributions (ms) of +6 charge state of 1:1 FGF1–HS complex and +12 charge state of 2:2 FGF1–HS complex, with HS4a (upper), HS4b (middle), and HS4c (lower). The comparison between the narrow, well-defined arrival distribution of 2:1 FGF1–HS dp4a complex and the broad arrival time distribution of 2:1 FGF1–HS dp4b complex or 2:1 FGF1–HS dp4c complex indicates that the high affinity binding motif is responsible for the level of specificity in the dimerization of FGF1 upon the binding of HS