Evaporation from water clusters containing singly charged ions

Molecular dynamics simulations were used to study the evaporation from water clusters containing either Cl(-), H(2)PO(4)(-), Na(+) or NH(4)(+) ions. The simulations ranged between 10 and 500 ns, and were performed in vacuum starting at 275 K. A number of different models were used including polarizable models. The clusters contain 216 or 512 molecules, 0, 4 or 8 of which were ions. The ions with hydrogen bonding properties do not affect evaporation, even though the phosphate ions have a pronounced ion-ion structure and tend to be inside the cluster whereas ammonium shows little ion-ion structure and has a distribution within the cluster similar to that of the water molecules. Since the individual ion-water interactions are much stronger in the case of Na(+)-water and Cl(-)-water clusters, evaporation is somewhat slower for clusters containing these ions. It seems therefore that the main determinant of the evaporation rate in ion-water clusters is the strength of the interaction. Fission of droplets that contain more ions than allowed according to the Rayleigh limit seems to occur more rapidly in clusters containing ammonium and sodium ions.     

Disintegration mechanisms of charged aqueous nanodroplets studied by simulations and analytical models

The mechanism of fragmentation processes in aqueous nanodroplets charged with ions is studied by molecular dynamics (MD) simulations. By using constant-temperature MD, the evaporation of the water is naturally taken into account and sequences of ion fragmentation events are observed. The size of the critical radius of the charged droplet just before the fragmentation and the distribution of the sizes of the fragments are estimated. Comparison of the Rayleigh critical radius for fragmentation and simulation data is within 0.23 nm. This seemingly small difference arises from a large difference in the number of water molecules that makes fragmentation an activated process as in the ion evaporation mechanism (IEM). This finding is in agreement with the predictions of Labowsky et al. [Anal. Chim. Acta 2000, 406, 105-118] for charged aqueous drops. The size of the daughter droplets is larger than the prediction of Born's theory by 0.1 to 0.15 nm. The nature and the dynamics of the intermediate states of the fragmentation process characterized by a bridge formed between the mother droplet and the evaporating ion or thorned structures where the ion sits on the tip are important for the outcome of the size-distribution of the fragments, while they are is missing in Born's theory.     

Nanojets, electrospray, and ion field evaporation: molecular dynamics simulations and laboratory experiments

The energetics, interfacial properties, instabilities, and fragmentation patterns of electrosprays made from formamide salt solutions are investigated in a mass spectrometric vacuum electrospray experiment and using molecular dynamics (MD) simulations. The electrospray source is operated in a Taylor cone-jet mode, with the nanojet that forms being characterized by high surface-normal electric field strengths in the vicinity of 1 V/nm. Mass-to-charge ratios were determined for both positive and negative currents sprayed from NaI-formamide solutions with solute-solvent mole ratios of 1:8.4 and 1:36.9, and from KI-formamide solutions with mole ratios of 1:41 and 1:83. The molecular dynamics simulations were conducted on isolated 10 nm NaI-formamide droplets at mole ratios of 1:8 and 1:16. The droplet was subjected to a uniform electric field with strengths ranging between 0.5 and 1.5 V/nm. Both the experiments and simulations demonstrate a mixed charge emission regime where field-induced desorption of solvated ions and charged droplets occurs. The macroscopic parameters, such as average mass-to-charge ratio and maximum surface-normal field strengths deduced from the simulations are found to be in good agreement with the experimental work and consistent with electrohydrodynamic theory of cone-jets. The observed mass spectrometric Na (+) and I (-) solvated ion distributions are consistent with a thermal evaporation process, and are correctly reproduced by the simulation after incorporation of the different flight times and unimolecular ion dissociation rates in the analysis. Alignment of formamide dipoles and field-induced reorganization of the positive and negative ionic charges in the interfacial region are both found to contribute to the surface-normal field near the points of charge emission. In the simulations the majority of cluster ions are found to be emitted from the tip of the jet rather than from the neck region next to the Taylor cone. This finding is consistent with the experimental energy distributions of the solvated ions which demonstrate that indeed most ions are emitted closer to the jet region, that is, beyond the cone-neck region where ohmic losses occur. This observation is also consistent with continuum electrohydrodynamic predictions of cluster-ion evaporation at surface regions of high curvature and therefore maximum surface electric field strengths, which may be the cone-neck region, the breakup region of the jet (usually near the tip of the jet), or the emitted charged droplets. In the nanoscale jets observed in this study, the regions of highest spatial curvature are at the ends of the jets where nascent drops either are forming or have just detached.     

Hydration of gas-phase ions formed by electrospray ionization

The hydration of gas-phase ions produced by electrospray ionization was investigated. Evidence that the hydrated ions are formed by two mechanisms is presented. First, solvent condensation during the expansion inside the electrospray source clearly occurs. Second, some solvent evaporation from more extensively solvated ions or droplets is apparent. To the extent that these highly solvated ions have solution-phase structures, then the final isolated gas-phase structure of the ion will be determined by the solvent evaporation process. This process was investigated for hydrated gramicidin S in a Fourier-transform mass spectrometer. Unimolecular dissociation rate constants of isolated gramicidin S ions with between 2 and 14 associated water molecules were measured. These rate constants increased from 16 to 230 s-1 with increasing hydration, with smaller values corresponding to magic numbers.     

The dynamics of water evaporation from partially solvated cytochrome c in the gas phase

The study of evaporation of water from biological macromolecules is important for the understanding of electrospray mass spectrometry experiments. In electrospray ionization (ESI), electrically charged nanoscale droplets are formed from solutions of, for example, proteins. Then evaporation of the solvent leads to dry protein ions that can be analyzed in the mass spectrometer. In this work the dynamics of water evaporation from native cytochrome c covered by a monolayer of water is studied by molecular dynamics (MD) simulations at constant energy. A model of the initial conditions of the process is introduced. The temperature of the protein drops by about 100 K during the 400 picoseconds of the simulations. This sharp drop in temperature causes the water evaporation rate to decrease by about an order of magnitude, leaving the protein with 50% to 90% of the original water molecules, depending on the initial temperature of the simulation. The structural changes of the protein upon desolvation were considered through calculations of the radius of gyration and the root mean square (RMS) of the protein. A variation of 0.4 A in the radius of gyration, together with an RMS value of less than 3 A, indicates only minor changes in the overall shape of the protein structure. The water coordination number of the solvation shell is much smaller than that for bulk water. The mobility of water is high at the beginning of the simulations and drops as the simulation progresses and the temperature decreases. Incomplete desolvation of protein ions was also observed in recent experiments.     

Ion-molecule reactions of ammonia clusters with C60 aggregates embedded in helium droplets

Helium nanodroplets are co-doped with C(60) and ammonia. Mass spectra obtained by electron ionization reveal cations containing ammonia clusters complexed with up to four C(60) units. The high mass resolution of Δm/m≈ 1/6000 makes it possible to separate the contributions of protonated, unprotonated and dehydrogenated ammonia. C(60) aggregates suppress the proton-transfer reaction which usually favors the appearance of protonated ammonia cluster ions. Unprotonated C(x)(NH(3))(n)(+) ions (x = 60, 120, 180) exceed the abundance of the corresponding protonated ions if n < 5; for larger values of n the abundances of C(60)(NH(3))(n)(+) and C(60)(NH)(n-1)NH(4)(+) become about equal. Dehydrogenated C(60)NH(2)(+) ions are relatively abundant; their formation is attributed to a transient doubly charged C(60)-ammonia complex which forms either by an Auger process or by Penning ionization following charge transfer between the primary He(+) ion and C(60). The abundance of C(x)NH(3)(+) and C(x)NH(4)(+) ions (x = 120 or 180) is one to two orders of magnitude weaker than the abundance of ions containing one or two additional ammonia molecules. However, a model involving evaporation of NH(3) or NH(4) from the presumably weakly bound C(x)NH(3)(+) and C(x)NH(4)(+) ions is at odds with the lack of enhancement in the abundance of C(120)(+) and C(180)(+). Mass spectra of C(60) dimers complexed with water complement a previous study of C(60)(H(2)O)(n)(+) recorded at much lower mass resolution.     

Insights into the Mechanism of Protein Electrospray Ionization From Salt Adduction Measurements

The mechanisms whereby protein ions are liberated from charged droplets during electrospray ionization (ESI) remain under investigation. Compact conformers electrosprayed from aqueous solution in positive ion mode likely follow the charged residue model (CRM), which envisions analyte release after solvent evaporation to dryness. The concentration of nonvolatile salts such as NaCl increases sharply within vanishing CRM droplets, promoting nonspecific pairing of Cl^- and Na⁺ with charged groups on the protein surface. For unfolded proteins, it has been proposed that ion formation occurs via the chain ejection model (CEM). During the CEM proteins are expelled from the droplet long before complete solvent evaporation has taken place. Here we examine whether salt adduction levels support the view that folded and unfolded proteins follow different ESI mechanisms. Solvent evaporation during the CEM is expected to be less extensive and, hence, the salt concentration at the point of protein release should be substantially lower than for the CRM. CEM ions should therefore exhibit lower adduction levels than CRM species. We explore the adduction behavior of several proteins that were chosen to allow comparative studies on folded and unfolded structures in the same solution. In-source activation eliminates chloride adducts via HCl release, generating protein ions that are heterogeneously charged because of sodiation and protonation. Sodiation levels measured under such conditions provide estimates of the salt adduction behavior experienced by the “nascent” analyte ions. Sodiation levels are significantly reduced for unfolded proteins, supporting the view that these species are indeed formed via the CEM.

Molecular dynamics simulations on the Escherichia coli ammonia channel protein AmtB: mechanism of ammonia/ammonium transport

Molecular dynamics (MD) simulations have been performed at the atomic level to study the ammonium/ammonia transport across the Escherichia coli AmtB membrane protein. Although ammonia primarily exists in the form of NH(4)(+) in aqueous solution, the recent X-ray structure determination of AmtB reveals that the ammonium/ammonia transporter proteins are ammonia-conducting channels rather than ammonium ion transporters [Khademi, S.; et al. Science 2004, 305, 1587; Zheng, L.; et al. Proc. Natl. Acad. Sci. U.S.A. 2004, 101, 17090]. Our simulations showed that the entrance of NH(4)(+) into the periplasmic recruitment vestibule requires only 3.1 kcal/mol of energy. This is consistent with the X-ray crystal structure, where one NH(4)(+) is captured in the binding vestibule. In this vestibule, NH(4)(+) loses one water of hydration, but the loss is compensated by a hydrogen bond, first with the backbone carbonyl oxygen of Phe161 then with the hydroxyl group of Ser219, as well as the stabilizing pi-cation interactions with the aromatic rings of Trp148 and Phe107 in the AmtB protein. In the end of this recruitment vestibule, the phenyl ring of Phe107 dynamically switches to an open state. This is correlated with a slight rotation and shifting of the indole ring of Trp148, which eventually creates a slot for the initially buried carboxylate group of Asp160 to become exposed to the bulk solvent. A hydrogen bond wire between NH(4)(+) and the carboxylate group of Asp160 via two water molecules was observed. Thus, Asp160 is most likely the proton acceptor from NH(4)(+). This explains the high conservation of Asp160 in Amt proteins and why the D160A mutant would completely quench the activity of AmtB [Javelle, A.; et al. J. Biol. Chem. 2004, 279, 8530; Marini, A. M.; et al. Curr. Genet. 2006, 49, 364]. Once NH(4)(+) deprotonates, the phenyl ring of Phe215 rotates to open, and the subsequent passage of NH(3) through the channel is straightforward.     

Gas-phase ion chemistry of BF(3)/NH(3) mixtures

The gas-phase ion chemistry of BF(3)/NH(3) mixtures was investigated by the joint application of mass-spectrometric techniques and theoretical methods. The addition of BF(2)(+) to NH(3) led to the first observation of [BF(2),NH(3)](+) and [BF,NH(2)](+) ions. Diamidoboron cation B(NH(2))(2)(+) was also detected. Consistent with collisionally activated dissociation (CAD) mass spectrometric results, theoretical calculations performed at the B3LYP and CCSD(T) levels identified the F(2)B-NH(3)(+), FB-NH(2)(+), and NH(2)-B-NH(2)(+) ions as the most stable isomers on the corresponding potential energy surfaces. The F(2)B-NH(3)(+) ion represents the protonated form of aminodifluoroborane, BF(2)NH(2), and consequently behaves as a Br?nsted acid under FT-ICR conditions. The FBNH(2)(+) ion is able to add Lewis bases such as water, ammonia, and hydrazoic acid. These species, containing the BN moiety, may represent new promising projectile ions in the boron nitride deposition techniques involving high-energy ion beams.     

Investigation of efflorescence of inorganic aerosols using fluorescence spectroscopy

The phase transition is one of the most fundamental phenomena affecting the physical and chemical properties of atmospheric aerosols. Efflorescence, in particular, is not well understood, partly because the molecular interactions between the solute and water molecules of saturated or supersaturated solution droplets have not been well characterized. Recently, we developed a technique that combines the use of an electrodynamic balance and a fluorescence dye, 8-hydroxyl-1,3,6-pyrenetrisulfonate (pyranine), to study the distributions of solvated and free water in aqueous droplets (Choi, M. Y.; Chan, C. K.; Zhang, Y. H. J. Phys. Chem. A 2004, 108, 1133). We found that the equality of the amounts of solvated and free water is a necessary but not sufficient condition for efflorescence. For efflorescing compounds such as Na2SO4, (NH4)2SO4, and a mixture of NaCl and Na2SO4, the amount of free water decreases, while that of solvated water is roughly constant in bulk measurements and decreases less dramatically than that of free water in single-particle measurements as the relative humidity (RH) decreases. Efflorescence of the supersaturated droplets of these solutions occurs when the amounts of free and solvated water are equal, which is consistent with our previous observation for NaCl. For nonefflorescing compounds in single-particle levitation experiments such as MgSO4 and Mg(NO3)2, the amounts of free and solvated water are equal at a water-to-solute molar ratio of about 6, at which spectral changes due to the formation of contact ion pairs between magnesium and the anions occur as shown by Raman spectroscopy. Fluorescence imaging shows that the droplets of diluted Mg(NO3)2 (at 80% RH) and MgSO4 are homogeneous but those of NaCl, Na2SO4, (NH4)2SO4, and supersaturated Mg(NO3)2 (at 10% RH) are heterogeneous in terms of the solvated-to-free water distribution. The solvated-to-free water ratios in NaCl, Na2SO4, and (NH4)2SO4 droplets are higher in the outer regions by about half a radius deep than at the center of the droplets.     

Molecular dynamics of electrosprayed water nanodroplets containing sodium bis(2‐ethylhexyl)sulfosuccinate

The behavior of aqueous solutions of sodium bis(2‐ethylhexyl)sulfosuccinate (AOTNa) subject to electrospray ionization (ESI) has been investigated by molecular dynamics (MD) simulations at three temperatures (350, 500 and 800 K). We consider several types of water nanodroplets containing AOTNa molecules and composed of a fixed number of water molecules (1000), N⁰_AOT AOT^? anions (N⁰_AOT = 0, 5, 10) and N⁰_Na sodium ions (N⁰_Na = 0, 5, 10, 15, 20): in a short time scale (less than 1 ns), the AOTNa molecules, initially forming direct micelles in the interior of the water nanodroplets, are observed in all cases to diffuse nearby the nanodroplet surface, so that the hydrophilic heads and sodium ions become surrounded by water molecules, whereas the alkyl chains lay at the droplet surface. Meanwhile, evaporation of water molecules and of solvated sodium ions occurs, leading to a decrease of the droplet size and charge. At 350 K, no ejection of neutral or charged surfactant molecules is observed, whereas at 500 K, some fragmentation occurs, and at 800 K, this event becomes more frequent. The interplay of all these processes, which depend on the values of temperature, N⁰_AOT and N⁰_Na eventually leads to anhydrous charged surfactant aggregates with prevalence of monocharged ones, in agreement with experimental results of ESI mass spectrometry. The quantitative analysis of the MD trajectories allows to evidence molecular details potentially useful in designing future ESI experimental conditions. Copyright © 2013 John Wiley & Sons, Ltd.     

A model for solvated ion emission from electrospray droplets

A model is presented which shows that the energy required to emit small singly charged and large multiply charged (protein) solvated ions from electrospray droplets can be considerably lower than those predicted by earlier models. By allowing the droplet surface to distort in reaction to the emerging ion, a more nuanced picture of the ion emission mechanism appears, one that covers the range from pure ion evaporation (PIE) for small ions to what may be termed activated pseudo-Rayleigh ion release (PRIR), a mechanism that yields charge states nearly indistinguishable from the charge residue model (CRM), for large ions. Predictions based on this model are qualitatively consistent with many experimentally observed trends.     

Molecular simulation analysis and X-ray absorption measurement of Ca2+, K+ and Cl- ions in solution

This paper presents recent advances in the use of molecular simulations and extended X-ray absorption fine structure (EXAFS) spectroscopy, which enable us to understand solvated ions in solution. We report and discuss the EXAFS spectra and related properties governing solvation processes of different ions in water and methanol. Molecular dynamics (MD) trajectories are coupled to electron scattering simulations to generate the MD-EXAFS spectra, which are found to be in very good agreement with the corresponding experimental measurements. From these simulated spectra, the ion-oxygen distances for the first hydration shell are in agreement with experiment within 0.05-0.1 A. The ionic species studied range from monovalent to divalent, positive and negative: K+, Ca2+, and Cl-. This work demonstrates that the combination of MD-EXAFS and the corresponding experimental measurement provides a powerful tool in the analysis of the solvation structure of aqueous ionic solutions. We also investigate the value of electronic structure analysis of small aqueous clusters as a benchmark to the empirical potentials. In a novel computational approach, we determine the Debye-Waller factors for Ca2+, K+, and Cl- in water by combining the harmonic analysis of data obtained from electronic structure calculations on finite ion-water clusters, providing excellent agreement with the experimental values, and discuss how they compare with results from a harmonic classical statistical mechanical analysis of an empirical potential.     

Atmospheric pressure electrospray ionization mass spectra of glucose and 2-fluorodeoxyglucose for quantitative analysis of 2-fluorodeoxyglucose by high-performance liquid chromatography

2-Fluoro-2-deoxy-D-glucose (FDG) labeled by fluorine-18 is the most widely used radiopharmaceutical for positron emission tomography (PET). For high-performance liquid chromatography (HPLC)/MS assay and quality control, the mass spectra of FDG and glucose (Glc) in organic + water solutions were studied by flow injection analysis (FIA) and in a chromatographic eluate. In acetonitrile (MeCN) + 0.025% ammonium formate (NH(4)HCO(2)) solvent (80 : 20), electrospray ionisation (ESI) of glucose-FDG provides M.NH(4)(+) and 2M.Na(+) (M = Glc or FDG) as the most intense positive ions. Formation of the latter ions and also of M.MeCN.Na(+) and 2MeCN. Na(+) is typical of the presence of NaCl in the ESI inlet. The positive ions include heavier ions corresponding to the impurities separated by HPLC and also to the cross-ring fragmentation of complexes (2FDG. aMeCNX)L, where a = 0 or 1, L is either Na(+) or NH(4)(+) and X is a fragmented pyranose or anhydropyranose residue. The second most abundant Glc negative ion is m/z = 359 which was interpreted as (2GlcH(+))(). The negative-ion spectrum of FDG has dominating lines due to FDG.HCO(2)() ions at m/z 227 and also (2FDGH(+))() at m/z 363. The m/z 363 signal is suppressed in the presence of NaCl at a molar ratio of 4 : 1 to NH(4)HCO(2), while the ions at m/z 217 and 219, i.e. FDG.Cl(), become three times more intense than FDG.HCO(2)(). The latter ion appears to be most suitable as an analytical signal for chemical analysis of FDG at m/z 226 and 227. Limits of FDG quantitation (LOQ) of 19 ng and 21 ng were found for the 200(+) and 227() ion signals, respectively, and are wholly adequate for verification of total FDG content in radiopharmaceuticals.     

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

Mechanistic information about how gaseous ions are formed from charged droplets has been difficult to establish because direct observation of nanodrops in a size range relevant to gaseous macromolecular ion formation by optical or traditional mass spectrometry methods is challenging owing to their small size and heterogeneity. Here, the mass and charge of individual aqueous nanodrops between 1–10 MDa (15–32 nm diameter) with ∼50–300 charges are dynamically monitored for 1 s using charge detection mass spectrometry. Discrete losses of minimally solvated singly charged ions occur, marking the first direct observation of ion emission from aqueous nanodrops in late stages of droplet evaporation relevant to macromolecular ion formation in native mass spectrometry. Nanodrop charge depends on the identity of constituent ions, with pure water nanodrops charged slightly above the Rayleigh limit and aqueous solutions containing alkali metal ions charged progressively below the Rayleigh limit with increasing cation size. MS2 capsid ions (∼3.5 MDa; ∼27 nm diameter) are more highly charged from aqueous ammonium acetate than from its biochemically preferred, 100 mM NaCl/10 mM Na phosphate solution, consistent with ion emission reducing the nanodrop and resulting capsid charge. The extent of charging indicates that the capsid partially collapses inside the nanodrops prior to the charging and formation of the dehydrated gaseous ions. These results demonstrate that ion emission can affect macromolecular charging and that conformational changes to macromolecular structure can occur in nanodrops prior to the formation of naked gaseous ions.

Ion evaporation from aqueous nanodrops is measured for the first time using charge detection mass spectrometry, and the origin of solute ion dependent charging of large (MDa) macromolecules is revealed.     

Solvation of perfluorooctane and octane in water, methanol, acetonitrile, and aqueous mixtures of methanol and acetonitrile

Molecular dynamics simulations are used to examine the local solvation structure of single octane and perfluorooctane molecules in liquid water, methanol, acetonitrile, and aqueous mixtures of methanol and acetonitrile. The motivation is to obtain baseline information about the solvation of perfluorooctane by liquids used as the mobile phase in liquid chromatography and how it differs from the solvation of octane. While octane is uniformly solvated by both water and the second component, perfluorooctane is solvated by methanol and acetonitrile with the exclusion of water from the first solvation layer when the solvent is a mixture.     

Absolute electrode potential and thermodynamics of single ions

A new method, relating the electrode potential to the radius of the solvated ion on whose activity the potential depends, has been developed for the determination of absolute electrode potentials and the thermodynamics of single ions in solution. It is successfully applied to the cells: Pt|H₂(g, 1 atm)|HX, solvent |AgX|Ag, and M|MX, solvent|AgX|Ag, in aqueous, partially aqueous, and non-aqueous solvents. The absolute electrode potentials have been computed in aqueous and methanol+water solvents. The single ion activities, activity coefficients, the radii of solvated cations, and their solvation extent have been calculated. The temperature variation of the standard absolute potential has been utilized to evaluate the standard thermodynamic functions for the electrode reactions, and the standard transfer thermodynamic quantities of single ions from water to methanolic solvents. The results are interpreted in terms of ion—solvent interactions as well as the structural features and the acid—base properties of these solvents.     

Dissection of the difference between the group I metal ions in inhibiting GSK3β: a computational study

Glycogen synthase kinase 3β (GSK3β) is a serine/threonine kinase that requires two cofactor Mg(2+) ions for catalysis in regulating many important cellular signals. Experimentally, Li(+) is a competitive inhibitor of GSK3β relative to Mg(2+), while this mechanism is not experienced with other group I metal ions. Herein, we use native Mg(2)(2+)-Mg(1)(2+) GSK3β and its Mg(2)(2+)-M(1)(+) (M = Li, Na, K, and Rb) derivatives to investigate the effect of metal ion substitution on the mechanism of inhibition through two-layer ONIOM-based quantum mechanics/molecular mechanics (QM/MM) calculations and molecular dynamics (MD) simulations. The results of ONIOM calculations elucidate that the interaction of Na(+), K(+), and Rb(+) with ATP is weaker compared to that of Mg(2+) and Li(+) with ATP, and the critical triphosphate moiety of ATP undergoes a large conformational change in the Na(+), K(+), and Rb(+) substituted systems. As a result, the three metal ions (Na(+), K(+), and Rb(+)) are not stable and depart from the active site, while Mg(2+) and Li(+) can stabilize in the active site, evident in MD simulations. Comparisons of Mg(2)(2+)-Mg(1)(2+) and Mg(2)(2+)-Li(1)(+) systems reveal that the inline phosphor-transfer of ATP and the two conserved hydrogen bonds between Lys85 and ATP, together with the electrostatic potential at the Li(1)(+) site, are disrupted in the Mg(2)(2+)-Li(1)(+) system. These computational results highlight the possible mechanism why Li(+) inhibits GSK3β.     

Solvation of acylium fragment ions in electrospray ionization quadrupole ion trap and Fourier transform ion cyclotron resonance mass spectrometry

In electrospray ionization (ESI) quadrupole ion trap and Fourier transform ion cyclotron resonance mass spectrometry, certain fragment ions (e.g. acylium ions) generated either during the ion transportation process (in the source interface region) or in the ion trap are found to undergo ion--molecule reactions with ESI solvent molecules (water, acetonitrile and aliphatic alcohols) to form adduct species. These unexpected solvated fragment ions severely complicate the interpretation of mass spectrometic data. High-resolution accurate mass measurements are important in establishing the elemental compositions of these adduct species and preventing erroneous data interpretation.