Sizing and discovery of nanosized polyoxometalate clusters by mass spectrometry

Surman, A. J. , Robbins, P. J., Ujma, J., Zheng, Q., Barran, P. E. and Cronin, L. (2016) Sizing and discovery of nanosized polyoxometalate clusters by mass spectrometry. Journal of the American Chemical Society, 138(11), pp. 3824-3830. (doi:10.1021/jacs.6b00070) (PMID:26906879) (PMCID:PMC5033399)

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Abstract

Ion mobility-mass spectrometry (IM-MS) is a powerful technique for structural characterization, e.g., sizing and conformation, particularly when combined with quantitative modeling and comparison to theoretical values. Traveling wave IM-MS (TW-IM-MS) has recently become commercially available to nonspecialist groups and has been exploited in the structural study of large biomolecules, however reliable calibrants for large anions have not been available. Polyoxometalate (POM) species—nanoscale inorganic anions—share many of the facets of large biomolecules, however, the full potential of IM-MS in their study has yet to be realized due to a lack of suitable calibration data or validated theoretical models. Herein we address these limitations by reporting DT-IM (drift tube) data for a set of POM clusters {M12} Keggin 1, {M18} Dawson 2, and two {M7} Anderson derivatives 3 and 4 which demonstrate their use as a TW-IM-MS calibrant set to facilitate characterization of very large (ca. 1–4 nm) anionic species. The data was also used to assess the validity of standard techniques to model the collision cross sections of large inorganic anions using the nanoscale family of compounds based upon the {Se2W29} unit including the trimer, {Se8W86O299} A, tetramer, {Se8W116O408} B, and hexamer {Se12W174O612} C, including their relative sizing in solution. Furthermore, using this data set, we demonstrated how IM-MS can be used to conveniently characterize and identify the synthesis of two new, i.e., previously unreported POM species, {P8W116}, unknown D, and {Te8W116}, unknown E, which are not amenable to analysis by other means with the approximate formulation of [H34W118X8M2O416]44–, where X = P and M = Co for D and X = Te and M = Mn for E. This work establishes a new type of inorganic calibrant for IM-MS allowing sizing, structural analysis, and discovery of molecular nanostructures directly from solution.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Cronin, Professor Leroy and Surman, Dr Andrew and Zheng, Ms Qi
Authors: Surman, A. J., Robbins, P. J., Ujma, J., Zheng, Q., Barran, P. E., and Cronin, L.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Journal of the American Chemical Society
Publisher:American Chemical Society
ISSN:0002-7863
Published Online:23 February 2016

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
577391Programmable Molecular Metal Oxides (PMMOs) - From Fundamentals to ApplicationLeroy CroninEngineering & Physical Sciences Research Council (EPSRC)EP/J015156/1CHEM - CHEMISTRY
646611Programmable 'Digital' Synthesis for Discovery and Scale-up of Molecules, Clusters and NanomaterialsLeroy CroninEngineering & Physical Sciences Research Council (EPSRC)EP/L023652/1CHEM - CHEMISTRY
562821Innovative Manufacturing Research Centre for Continuous Manufacturing and Crystallisation (CMAC)Leroy CroninEngineering & Physical Sciences Research Council (EPSRC)EP/I033459/1CHEM - CHEMISTRY
577391Programmable Molecular Metal Oxides (PMMOs) - From Fundamentals to ApplicationLeroy CroninEngineering & Physical Sciences Research Council (EPSRC)EP/J015156/1CHEM - CHEMISTRY
616021Energy and the Physical Sciences: Hydrogen Production using a Proton Electron BufferLeroy CroninEngineering & Physical Sciences Research Council (EPSRC)EP/K023004/1CHEM - CHEMISTRY
646611Programmable 'Digital' Synthesis for Discovery and Scale-up of Molecules, Clusters and NanomaterialsLeroy CroninEngineering & Physical Sciences Research Council (EPSRC)EP/L023652/1CHEM - CHEMISTRY
599451Microscale Chemically Reactive Electronic AgentsLeroy CroninEuropean Commission (EC)FP7 ICT MICRE31CHEM - CHEMISTRY