Charging and supercharging of proteins for mass spectrometry: recent insights into the mechanisms of electrospray ionization

Konermann, Lars; Metwally, Haidy; Duez, Quentin; Peters, Insa

doi:10.1039/c9an01201j

Cited by 63 publications

(195 citation statements)

References 158 publications

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“…The participation of Cl − -ion in adducts under ESI-MS experimental conditions has been observed previously [99]. Figure B3 shows the energetics of clusters of multiply charged ions together with selected optimized geometry parameters.…”

Section: Interionic/intermolecular Interactions Of Clusters and Multisupporting

confidence: 52%

Electrospray ionization mass spectrometric solvate cluster and multiply charged ions: a stochastic dynamic approach to 3D structural analysis

Ivanova

Spiteller

2020

SN Appl. Sci.

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The data analyzed in this paper are on quantitative and 3D structural determination of ionic ensembles and multiply charged solvates ions of type [(Cl)(H 2 O) x (H 3 O) y (CH 3 CN) z ] + , [(Cl)(O 2) x (CH 3 OH) y (NH 4) z ] + , [(O 2) x (H 2 O)(H 3 O)(CH 3 CN)] + n and [(Cl) (H 2 O) 2 (H 3 O)(CH 3 CHN 2)] + observable under electrospray ionization conditions in presence of Zn II-ion containing metalorganics, where x = y = z = 1-3 are the number of molecules, respectively, ions participating into each of the interacting ensemble, while "n" denotes the number of interacting ensembles forming the more complex ionic clusters. The major theoretical problem we have to deal with is the applicability of our more recently developed stochastic dynamic concept and formulas connecting among the mass spectrometric variable intensity, the so-called stochastic dynamic diffusion parameters (D SD), the temperature (T) and the analyte concentration in solution to such challenging molecular/ionic systems from the perspective of molecular structure. The D SD parameters of analyte ions correlate linearly with the socalled quantum chemical diffusion parameters (D QC) according to the Arrhenius's theory. The work has demonstrated persuasively that these equations are capable of providing reliable analytical information about so complex ensembles of interacting species. It shows their significant advantages as analytical approaches, amongst other rival concepts, to quantify the mass spectrometric outcome intensity highly accurately, selectively, precisely and sensitively. The thermodynamics parameters of common reactions of the following ionic species observable under electrospray ionization experimental conditions of some tetrachlrozinc(II) complex ions of metal-organics are examined. These are the ions [(Cl) (H 2 O)(H 3 O) 2 (CH 3 CN) 3 ] + (m/z 214/216), [(Cl)(H 2 O)(H 3 O) 2 (CH 3 CN) 2 ] + (m/z 173/175), [(Cl)(H 2 O) 2 (H 3 O) 2 (CH 3 CN)] + (m/z 150/152), [(Cl)(H 2 O)(H 3 O) 2 (CH 3 CHNH] + (m/z 134/136,) [(Cl)(H 2 O) 2 (H 3 O)(CH 3 CHNH 2 ] + , [(Cl)(H 2 O)(H 3 O) 2 (CH 3 CN] + (m/z 132/134,) [(Cl) (H 2 O) 2 (H 3 O) 2 (CH 3 CN] + (m/z 183/185), [(CH 3 OH)(H 2 O) 5 (NH 4)(CH 3 CN) 3 ] + 3 (m/z 263,) and [(CH 3 OH)(H 2 O)(H 3 O)(CH 3 CN)] + 31 (m/z 110,) respectively.

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Section: Interionic/intermolecular Interactions Of Clusters and Multisupporting

confidence: 52%

Electrospray ionization mass spectrometric solvate cluster and multiply charged ions: a stochastic dynamic approach to 3D structural analysis

Ivanova

Spiteller

2020

SN Appl. Sci.

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“…In the EDDA solution (pH 8), the dominant charge state distribution (CSD) includes 20+ and 19+ charge states, while in AmAc (pH 7) we observed a distribution of higher charge states, with dominant 23+ and 22+ charge states; this charge state difference is consistent with previous findings. 38,39,47,48 In the presence of roughly ½ equivalents of Trp per binding site (~5.5 equivalents per TRAP11 ring), we observe for each charge state a series of well-separated peaks that correspond to the mass of TRAP11 with varying numbers of bound Trp (from 0 to 11). In either AmAc or EDDA, spectra yielded narrow charge state distributions and well-resolved peaks corresponding to similar distributions of Trp( 0-11)-TRAP11 states.…”

Section: Choice Of Electrolyte Solution Does Not Significantly Affect Measurement Of Trp-trap Binding By Native Msmentioning

confidence: 91%

Population Distributions from Native Mass Spectrometry Titrations Reveal Nearest-Neighbor Cooperativity in the Ring-Shaped Oligomeric Protein TRAP

et al. 2020

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Allostery pervades macromolecular function and drives cooperative binding of ligands to macromolecules. To decipher the mechanisms of cooperative ligand binding it is necessary to define, at a microscopic level, the thermodynamic consequences of binding of each ligand to its energetically coupled site(s). However, extracting these microscopic constants is difficult for macromolecules with more than two binding constants. This goal is complicated because the observable (e.g., NMR chemical shift changes, fluorescence, enthalpy) can be altered by allostery, thereby distorting its proportionality to populations of states. Because it measures mass, native mass spectrometry (MS) can directly quantify the populations of homo-oligomeric protein species with different numbers of bound ligands, provided the populations are proportional to ion counts and that MS-compatible electrolytes do not alter the overall thermodynamics. These measurements can help decipher allosteric mechanisms by providing unparalleled access to the statistical thermodynamic partition function. We used native MS (nMS) to study the cooperative binding of tryptophan (Trp) to Bacillus stearothermophilus trp RNA-binding attenuation protein (TRAP), a ring-shaped homo-oligomeric protein complex with 11 identical binding sites. Mass spectrometrycompatible solutions did not significantly perturb protein structure and thermodynamics as assessed by ITC and NMR spectroscopy. Populations of Trpn-TRAP11 states were quantified as a function of Trp concentration by native mass spectrometry.Population distributions cannot be explained by a non-cooperative binding model but are well described by a nearest neighbor cooperative model. Non-linear least-squares fitting of the populations to a mechanistic model yielded microscopic thermodynamic constants that define the interactions between neighboring binding sites that result in homotropic cooperativity in Trp binding to TRAP. File list (2) download file view on ChemRxiv TrpTRAP_manuscript_mainbody-mf.pdf (1.22 MiB) download file view on ChemRxiv PLH_20200428_TrpTRAP_suppinfo.pdf (0.96 MiB)

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“…4,5,20,[22][23][24] Molecular dynamics (MD) simulations support ion evaporation of Na + and other small ions from nanodrops with diameters <5.5 nm. [22][23][24] For droplets that contain larger analytes, results from MD simulations suggest the possibility of several different mechanisms. Simulations by Consta and co-workers indicate that droplets that contain a DNA or RNA ion can distort into "star" morphologies in the late stages of desiccation.…”

Section: Introductionmentioning

confidence: 99%

Direct observation of ion emission from charged aqueous nanodrops: effects on gaseous macromolecular charging

et al. 2021

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Charging and supercharging of proteins for mass spectrometry: recent insights into the mechanisms of electrospray ionization

Abstract: Molecular dynamics simulations have uncovered mechanistic details of the protein ESI process under various experimental conditions.

Cited by 63 publications

References 158 publications

Electrospray ionization mass spectrometric solvate cluster and multiply charged ions: a stochastic dynamic approach to 3D structural analysis

Electrospray ionization mass spectrometric solvate cluster and multiply charged ions: a stochastic dynamic approach to 3D structural analysis

Population Distributions from Native Mass Spectrometry Titrations Reveal Nearest-Neighbor Cooperativity in the Ring-Shaped Oligomeric Protein TRAP

Direct observation of ion emission from charged aqueous nanodrops: effects on gaseous macromolecular charging

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