title: Characterization of Metallosupramolecular Polymers by Top-Down Multidimensional Mass Spectrometry Methods.
abstract: Top-down multidimensional mass spectrometry, interfacing electrospray ionization (ESI) with ion mobility mass spectrometry (IM-MS), and energy resolved (gradient) tandem mass spectrometry (gMS(2) ) are employed to characterize the stoichiometries, architectures, and intrinsic stabilities of coordinatively bound supramolecular polymers containing terpyridine functionalized ligands. As a soft ionization method, ESI prevents or minimizes unwanted assembly destruction. The IM dimension affords separation of the supramolecular ions by charge and collision cross-section (a function of size and shape). The mobility separated ions are subsequently identified by their mass-to-charge-ratios and isotope patterns in the orthogonal MS dimension. Finally, the gMS(2) dimension reveals bond breaking proclivities and disintegration pathways of the assemblies. The described methodology does not require high sample purity due to the dispersive nature of the IM and MS steps. Its utility is demonstrated with the comprehensive analysis of bisterpyridine-based metallomacrocycle mixtures and a tristerpyridine based complex with 3-D nanosphere-like architecture.
authors.affiliation: Department of Polymer Science, The University of Akron, Akron, OH, 44325, USA.
authors.forename: Kai
authors.initials: K
authors.lastname: Guo
authors.affiliation: Department of Chemistry, The University of Akron, Akron, OH, 44325, USA.
authors.forename: Zaihong
authors.initials: Z
authors.lastname: Guo
authors.affiliation: Department of Polymer Science, The University of Akron, Akron, OH, 44325, USA.
authors.forename: James M
authors.initials: JM
authors.lastname: Ludlow
authors.affiliation: Department of Polymer Science, The University of Akron, Akron, OH, 44325, USA.
authors.forename: Tingzheng
authors.initials: T
authors.lastname: Xie
authors.affiliation: Department of Polymer Science, The University of Akron, Akron, OH, 44325, USA.
authors.forename: Shengyun
authors.initials: S
authors.lastname: Liao
authors.affiliation: Departments of Chemistry and Polymer Science, The University of Akron, Akron, OH, 44325, USA.
authors.forename: George R
authors.initials: GR
authors.lastname: Newkome
authors.affiliation: Departments of Chemistry and Polymer Science, The University of Akron, Akron, OH, 44325, USA.
authors.forename: Chrys
authors.initials: C
authors.lastname: Wesdemiotis
mesh_terms: D049329:Nanostructures; D011108:Polymers / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*
chemical_list: D011108:Polymers
keywords: gradient tandem mass spectrometry; ion mobility mass spectrometry; multidimensional mass spectrometry; supramolecular equilibrium; supramolecular reactivity