Rabbit metallothionein (MT) 2A complexes with Cd(II), Zn(II), Ag(I), Cu(I), Hg(II), arsenite, monomethylarsonous acid (MMA), and dimethylarsinous acid (DMA) have been examined using ion-mobility measurements and mass spectrometry in a triple-quadrupole mass spectrometer equipped with a segmented second quadrupole that doubled as an ion-mobility cell [Guo, Y.; Wang, J.; Javahery, G.; Thomson, B. A.; Siu, K. W. M. An Ion-Mobility Spectrometer with Radial Collisional Focusing. Anal. Chem. 2005, 77, 266 -275]. The metal ions confer conformational rigidity on the MT complexes, which counteracts Coulombic repulsion among protons added as a result of electrospray. Triply and quadruply protonated Cd 7 MT2A have smaller cross-sections than the Cd 7 MT2A structure deduced from published NMR data. For the 6ϩ ions, the As 6 MT2A complex has a cross-section of 790 Å 2 ; the MMA 10 MT2A complex, 920 Å 2 ; and the DMA 20 MT2A complex, 1220 Å 2 . This increase in cross-section of the As(III) species, from As 3ϩ to MMA to DMA, is interpreted as a consequence of decreasing multiple coordination and increasing number of methyl groups. I on mobility, K, is a measure of the ion's effective size by virtue of its collision cross-section, ⍀ T , at temperature T, with a given buffer gas, typically helium, under the influence of a weak electric field. Provided that the number density of the buffer gas, N, is sufficiently high and the imposed electric field, E, is sufficiently low, the drift velocity, v d , is proportional to E with K being the proportionality constant.⍀ T can be determined from K using the Mason-Schamp equation [1, 2]:where z is the numerical charge, e is the elementary charge, is the reduced mass of the ion and helium, and k is the Boltzmann's constant.The collision cross-section of an ion is one of the most readily measurable, albeit somewhat crude, structure-related parameter that has come under close scrutiny in the last decade or so. Coupled to comparisons with theoretical cross-sections calculated from probable structures found by optimizations using molecular dynamics and first-principle methods, measurements of ⍀ T have allowed insights into three-dimensional structures of peptides and proteins in the gas-phase [3][4][5].Ion-mobility measurements are typically made in drift tubes at atmospheric or subatmospheric pressure containing a stack of ring electrodes which maintain a constant electric field in the axial direction [6]. Highresolution operation requires the use of high (nearatmospheric) pressure and high voltages; the need for high pressure in the drift tube necessitates the use of small apertures in interfacing with the mass-analyzer region of the spectrometer (which requires lowpressure operation) and leads to radial diffusion because of increased ion residence time. This combination typically results in modest sensitivity. Recently, we reported construction and testing of an ion-mobility spectrometer that has its mobility cell as a 20-segment rf-only quadrupole and functionally the second quadrupole (q2)...