MP and CD-MS may overcome certain limitations of native MS in the
mass measurements of highly heterogeneous antibody–antigen
complexes. (A) MP provides an average mass for IgG1 (upper panel)
and sEGFR (middle) and is not hampered by the high micro-heterogeneity
of the latter. When 2 μM IgG1 was incubated with 5 μM
of sEGFR to form (IgG1)1:(sEGFR)1 and (IgG1)1:(sEGFR)2 complexes, jump dilution MP could resolve
these highly heterogeneous species (lower). (B) Although native MS
on samples at the same concentrations provided superior mass resolution
and accuracy for free IgG1 (upper), resolving individual glycoforms
(zoom), the high microheterogeneity of sEGFR, measured separately
(middle) and in antibody–antigen complexes (lower), resulted
in unresolved features. In these experiments, overlapping charge states
prevented mass measurements of these species. (C) More accurate masses
could be obtained by native CD-MS, measuring in two dimensions m/z and z (insets) for
sEGFR (upper) and all co-occurring species involving IgG1 and sEGFR
(lower). For these experiments, the same native MS samples were diluted
20-fold, leading to re-equilibration and thus a lower binding occupancy.