Electrospray ionization of large multiply charged species proceeds via Dole’s charged residue mechanism

Mora, Juan Fernández de la

doi:10.1016/s0003-2670(99)00601-7

Cited by 455 publications

(436 citation statements)

References 33 publications

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“…Capillary forces are expected to be dominant since the drop and the solute ion are typically charged below the Rayleigh limit. 2 However, capillary forces seem to dominate also for our GroEL complex, charged clearly above the Rayleigh limit. This is apparent from the fact that supercharged GroEL is more compact than most other proteins [1,9], while a deformable ion charged above its Rayleigh limit would stretch considerably [11].…”

Section: Capillary Compactionmentioning

confidence: 76%

“…(2) The maximum charge state observed is z= 82, substantially larger than the maximum theoretical Rayleigh charge [Equation (1)] expected for a water drop with the same volume as the GroEL ion. This is a highly unusual situation for proteins electrosprayed from neutral aqueous solutions [2] z max ¼ 0:0778 m 1=2 $ 71 ð1Þ…”

Section: Explanation For the Two Conformers Based On A Bimodal Chargementioning

confidence: 99%

“…Two Levels of Supercharging One possible mechanism leading to a dual mode of charging is suggested by observations (2) and (3). There is an unusual mechanism peculiar to GroEL enabling it to be charged substantially above z max (2), while this mechanism is exploited almost twice as intensely by one conformer than by the other (3). For brevity we will use the term supercharged or supercharging to refer to ions holding more charge than the Rayleigh charge on a spherical solvent drop of the same volume.…”

Section: Why Two Distinct Charge Distributionsmentioning

confidence: 99%

“…Therefore, the observed supercharging mechanism must be associated to the nonspherical shape of native GroEL. It is well known that linear polymer chains and denatured proteins can take far more charge than globular proteins [2]. The probable reason for this phenomenon is that the non-spherical object enables (or even forces) a nonspherical shape in the drop carrying it, which in turn allows this drop to sustain a charge above the Rayleigh limit.…”

Section: Why Two Distinct Charge Distributionsmentioning

confidence: 99%

“…In one picture put forth by Fenn and colleagues [3,4] a PEG ion would spread on the drop surface and bind to a number of free surface charges. When the drop has shrunk sufficiently for all of its free charges to be tied to the polymer, as it reaches the Rayleigh limit, the drop can no longer eject any net charge, nor can it remain spherical, which leads to a supercharged non-spherical drop [2]. This mechanism leading to charge levels substantially above the Rayleigh limit would apply not only to PEG, but also to other ions capable of extending widely and of binding charge, including denatured proteins.…”

Section: Why Two Distinct Charge Distributionsmentioning

confidence: 99%

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Why do GroEL Ions Exhibit Two Gas Phase Conformers?

Mora

2012

J. Am. Soc. Mass Spectrom.

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The reasons for the existence of two gas phase conformers for electrosprayed ions of the large tetradecameric protein complex GroEL are considered. Key features are that: (1) both conformers extrapolate to very similar cross sections in the limit of zero charge; (2) both conformers supercharge above the maximum value permitted by the Rayleigh criterion; and (3) one of the conformers supercharges substantially more than the other. We hypothesize that the supercharging observed is associated to the approximately cylindrical shape of GroEL in aqueous solution, enabling accumulation of extra charge on either one or two of its bases when they intersect the evaporating drop surface. The two conformers would then correspond to cases when either one or the two bases of the cylinder carry extra charge. Apparently, the conformer symmetrically (doubly) supercharged on both ends is Coulombically stretched, therefore exhibiting a mobility different from the conformer asymmetrically supercharged only on one end. Several general consequences follow. First, non-spherical proteins may generally be charged above the usual Rayleigh limit. Second, we confirm the previously advanced but contentious notion that gas phase protein ions are readily compacted or stretched away from their crystal structure by capillary and Coulombic forces during the electrospraying process.

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Section: Capillary Compactionmentioning

confidence: 76%

Section: Explanation For the Two Conformers Based On A Bimodal Chargementioning

confidence: 99%

Section: Why Two Distinct Charge Distributionsmentioning

confidence: 99%

Section: Why Two Distinct Charge Distributionsmentioning

confidence: 99%

Section: Why Two Distinct Charge Distributionsmentioning

confidence: 99%

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Why do GroEL Ions Exhibit Two Gas Phase Conformers?

Mora

2012

J. Am. Soc. Mass Spectrom.

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Native Mass Spectrometry as a Tool in Structural Biology

Lorenzen

Duijn

2010

CP Protein Science

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Native mass spectrometry (native MS) gives information about the composition, topological arrangements, dynamics, and structural properties of protein complexes. The mass range is principally unlimited and highly dynamic, allowing the detection of small subunits and large complexes within the same measurement. The amount of protein needed for an analysis is, compared to most other structural biology methods, very low. This unit provides an introduction to native MS. It starts with an explanation of the basic method and details on how to measure intact proteins and protein complexes, and continues with the study of dynamics and complex stability in the gas phase. The final section discusses the most recent extension to the native MS field, ion mobility, which allows the direct assessment of the structural properties of the complexes of interest.

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Some tenets pertaining to electrospray ionization mass spectrometry

2000

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The field of electrospray ionization mass spectrometry is reviewed with emphasis placed upon advances in the elucidation of fundamental mechanistic aspects of the ionization process that have been reported over the past 10 years. The analytical consequences of these findings are also examined. Eight central conclusions or 'tenets' are presented, as deduced from the body of work contained in 80 references.

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Electrospray ionization of large multiply charged species proceeds via Dole’s charged residue mechanism

Cited by 455 publications

References 33 publications

Why do GroEL Ions Exhibit Two Gas Phase Conformers?

Why do GroEL Ions Exhibit Two Gas Phase Conformers?

Native Mass Spectrometry as a Tool in Structural Biology

Some tenets pertaining to electrospray ionization mass spectrometry

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