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Physical Sciences and Mathematics Commons

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Chemistry

Western University

Chemistry Publications

2021

Ions

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Full-Text Articles in Physical Sciences and Mathematics

Mobile Protons Limit The Stability Of Salt Bridges In The Gas Phase: Implications For The Structures Of Electrosprayed Protein Ions., Lars Konermann, Elnaz Aliyari, Justin H Lee Apr 2021

Mobile Protons Limit The Stability Of Salt Bridges In The Gas Phase: Implications For The Structures Of Electrosprayed Protein Ions., Lars Konermann, Elnaz Aliyari, Justin H Lee

Chemistry Publications

Electrosprayed protein ions can retain native-like conformations. The intramolecular contacts that stabilize these compact gas-phase structures remain poorly understood. Recent work has uncovered abundant salt bridges in electrosprayed proteins. Salt bridges are zwitterionic BH+/A- contacts. The low dielectric constant in the vacuum strengthens electrostatic interactions, suggesting that salt bridges could be a key contributor to the retention of compact protein structures. A problem with this assertion is that H+ are mobile, such that H+ transfer can convert salt bridges into neutral B0/HA0 contacts. This possible salt bridge annihilation puts into question the …


Sulfolane-Induced Supercharging Of Electrosprayed Salt Clusters: An Experimental/Computational Perspective., Leanne M Martin, Lars Konermann Feb 2021

Sulfolane-Induced Supercharging Of Electrosprayed Salt Clusters: An Experimental/Computational Perspective., Leanne M Martin, Lars Konermann

Chemistry Publications

It is well-known that supercharging agents (SCAs) such as sulfolane enhance the electrospray ionization (ESI) charge states of proteins, although the mechanistic origins of this effect remain contentious. Only very few studies have explored SCA effects on analytes other than proteins or peptides. This work examines how sulfolane affects electrosprayed NaI salt clusters. Such alkali metal halide clusters have played a key role for earlier ESI mechanistic studies, making them interesting targets for supercharging investigations. ESI of aqueous NaI solutions predominantly generated singly charged [NanI(n-1)]+ clusters. The addition of sulfolane resulted in abundant …