On the evaporation of small ions from charged droplets
15 Mar 1976-Journal of Chemical Physics (American Institute of Physics)-Vol. 64, Iss: 6, pp 2287-2294
TL;DR: In this paper, a theoretical argument is developed to find in which conditions this ion evaporation can occur; to that end solvation free enthalpies of cluster ions are derived from existing experimental data and the absolute reaction rate theory is applied.
Abstract: Experiments are briefly reported which show that small ions separate or ’’evaporate’’ from evaporating droplets carrying electrical charges. A theoretical argument is developed to find in which conditions this ion evaporation can occur; to that end solvation free enthalpies of cluster ions are derived from existing experimental data and the absolute reaction rate theory is applied. The conditions for ion evaporation are compared with those for Rayleigh instability and it is shown that the first process should occur only when the drop reaches sizes of the order of 10−6 cm. The ion evaporation process must be operative in the evaporation of highly electrified cloud droplets when their solute concentration is low.
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TL;DR: Spectra have been obtained for biopolymers including oligonucleotides and proteins, the latter having molecular weights up to 130,000, with as yet no evidence of an upper limit.
Abstract: Electrospray ionization has recently emerged as a powerful technique for producing intact ions in vacuo from large and complex species in solution. To an extent greater than has previously been possible with the more familiar "soft" ionization methods, this technique makes the power and elegance of mass spectrometric analysis applicable to the large and fragile polar molecules that play such vital roles in biological systems. The distinguishing features of electrospray spectra for large molecules are coherent sequences of peaks whose component ions are multiply charged, the ions of each peak differing by one charge from those of adjacent neighbors in the sequence. Spectra have been obtained for biopolymers including oligonucleotides and proteins, the latter having molecular weights up to 130,000, with as yet no evidence of an upper limit.
6,765 citations
TL;DR: Electrospray (E S ) ionization has recently shown itself capable of producing intact ions, with multiple charges, from remarkably large, complex, and fragile parent species as mentioned in this paper, which is the state-of-the-art in mass spectrometric analysis.
Abstract: Chemistry has its origins as a quantitative science in the careful weighing of products and reactants by Lavoisier and his followers beginning some 200 years ago. Ever since then, the constantly evolving gravimetric balance has been a faithful servant of the laboratory chemist and has played a major role in developing the analytical methods that are the foundation of contemporary chemical science. Perhaps the ultimate stage in the evolution of that balance is represented by the modern mass spectrometer. It is able to determine with high precision the masses of individual atoms and molecules by transforming them into ions and measuring the response of their trajectories in vacuo to various combinations of electric and magnetic fields. Clearly, the sine qua non of such mass determination is the transformation of analyte atoms and molecules from their initial state in a sample to ions in vacuo ready for ”weighing.” Over the years, ingenious investigators have produced a variety of methods for achieving this transformation. One of them, electrospray ( E S ) ionization, has recently shown itself capable of producing intact ions, with multiple charges, from remarkably large, complex, and fragile parent species. Our assignment here is to review what has thus far been learned about this still uncommon technique and what it seems able to offer practitioners of mass spectrometric analysis. Our approach will be to set forth the present state of the ES ionization art in terms of a sort of menu of its procedures, processes, performance, and promise. Until very recently we have been almost the only group that has worked with ES ionization since the pioneering efforts of Malcolm Dole (1) some 20 years ago. Consequently, this review is more tutorial than most. Moreover, it may seem like a cook book that is overly preoccupied with the authors’ own culinary adventures. The reasoil is that many of the dishes to be described were first tried out in our own kitchen. Therefore, we earnestly urge the reader to remember what every gourmet knows: the piquancy of any dish on a bill of fare is due much less to its ingredients than to the skill of the chef whc. prepares it.
1,487 citations
TL;DR: L'effluent de chromatographie en phase liquide projete electrostatiquement dans un bain de gaz froid cree une dispersion de gouttelettes chargees qui s'evapore rapidement.
Abstract: L'effluent de chromatographie en phase liquide projete electrostatiquement dans un bain de gaz froid cree une dispersion de gouttelettes chargees qui s'evapore rapidement. Lorsque les gouttelettes deviennent plus petites, l'augmentation de la densite de charge superficielle et la baisse du rayon de courbure creent un champ suffisamment fort pour desorber les ions du solute. Une partie passe a travers un canal et forme un jet libre supersonique, puis passera dans l'analyseur de masse
1,476 citations
TL;DR: Fundamental studies of the ESI process are reviewed that are relevant to issues related to analyte chargeability and surface activity, and how accessible parameters such as nonpolar surface area and reversed phase HPLC retention time can be used to predict relative ESI response.
Abstract: In accomplishing successful electrospray ionization analyses, it is imperative to have an understanding of the effects of variables such as analyte structure, instrumental parameters, and solution composition. Here, we review some fundamental studies of the ESI process that are relevant to these issues. We discuss how analyte chargeability and surface activity are related to ESI response, and how accessible parameters such as nonpolar surface area and reversed phase HPLC retention time can be used to predict relative ESI response. Also presented is a description of how derivitizing agents can be used to maximize or enable ESI response by improving the chargeability or hydrophobicity of ESI analytes. Limiting factors in the ESI calibration curve are discussed. At high concentrations, these factors include droplet surface area and excess charge concentration, whereas at low concentrations ion transmission becomes an issue, and chemical interference can also be limiting. Stable and reproducible non-pneumatic ESI operation depends on the ability to balance a number of parameters, including applied voltage and solution surface tension, flow rate, and conductivity. We discuss how changing these parameters can shift the mode of ESI operation from stable to unstable, and how current-voltage curves can be used to characterize the mode of ESI operation. Finally, the characteristics of the ideal ESI solvent, including surface tension and conductivity requirements, are discussed. Analysis in the positive ion mode can be accomplished with acidified methanol/water solutions, but negative ion mode analysis necessitates special constituents that suppress corona discharge and facilitate the production of stable negative ions.
1,260 citations
Cites background from "On the evaporation of small ions fr..."
...A second mechanism, known as ion evaporation, assumes that the increased charge density that results from solvent evaporation eventually causes coulombic repulsion to overcome the liquid’s surface tension, resulting in a release of ions from droplet surfaces (Iribarne & Thomson, 1976)....
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TL;DR: Fundamental considerations suggest even more impressive developments may be anticipated related to detection sensitivity and methods for obtaining structural information, as well as new developments related to ESI-MS.
Abstract: The principles, development, and recent application of electrospray ionization-mass spectrometry (ESI-MS) to biological compounds are reviewed. ESI-MS methods now allow determination of accurate molecular weights for proteins extending to over 50,000, and in some cases well over 100,000. Similar capabilities are being developed for oligonucleotides. The instrumentation used for ESI-MS is briefly described and it is shown that, although ionization efficiency appears to be uniformly high, detector sensitivity may be directly correlated with molecular weight. The use of tandem mass spectrometry (e.g., MS/MS) for extending collision-induced dissociation (CID) methods to the structural studies of large molecules is described. For example, effective CID of various albumin species (molecular weight approximately 66,000) can be obtained, far larger than obtainable for singly charged molecular ions. The combination of capillary electrophoresis, in both free solution zone electrophoresis and isotachophoresis formats, as well as microcolumn liquid chromatography with ESI-MS, provides the capability for on-line separation and analysis of subpicomole quantities of proteins. These and other new developments related to ESI-MS are illustrated by a range of examples. Fundamental considerations suggest even more impressive developments may be anticipated related to detection sensitivity and methods for obtaining structural information.
1,041 citations
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01 Nov 2011TL;DR: In this paper, the authors focus on topics at the forefront of electrochemical research, such as splitting water by electrolysis, splitting water with visible light, and the recent development of lithium batteries.
Abstract: This book focuses on topics at the forefront of electrochemical research. Splitting water by electrolysis; splitting water by visible light; the recent development of lithium batteries; theoretical approaches to intercalation; and fundamental concepts of electrode kinetics, particularly as applied to semiconductors are discussed. It is recommended for electrochemists, physical chemists, corrosion scientists, and those working in the fields of analytical chemistry, surface and colloid science, materials science, electrical engineering, and chemical engineering.
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TL;DR: McDaniel et al. as mentioned in this paper presented a series of experiments in Atomic and Molecular Collisional Processes (AOMCPs) and showed that collisional processes can be solved by ion reactions.
Abstract: Ion Molecule Reactions By E. W. McDaniel, V. Cermak, A. Dalgarno, E. E. Ferguson and L. Friedman. (Wiley Interscience Series in Atomic and Molecular Collisional Processes.) Pp. xiii + 374. (Wiley (Interscience): New York and London, August 1970.) 190s.
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