Recombination of Gaseous Ions

Prigogine, I.; Rice, Stuart A.; Mahan, Bruce H.

doi:10.1002/9780470143735.ch1

Cited by 59 publications

(9 citation statements)

References 51 publications

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“…The square of the impact parameter (in atomic units) takes the form [55]:

b_{E T}^{2} = r_{E T}^{2} [1 + \frac{2 ∣ Z_{cat} Z_{a n} ∣}{r_{E T} μ v_{rel}^{2}}]

where Z cat and Z an are the unit charges of the cationic and anionic reactants, respectively; ν rel is the relative velocity of the ions; μ is the reduced mass of the collision partners; and r ET is the distance at which the electron transfer occurs. In this work, Z cat =2+ and Z an =1− in all experiments.…”

Section: Resultsmentioning

confidence: 99%

Cation Recombination Energy/Coulomb Repulsion Effects in ETD/ECD as Revealed by Variation of Charge per Residue at Fixed Total Charge

Mentinova

Crizer

Baba

et al. 2013

J. Am. Soc. Mass Spectrom.

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Electron capture dissociation (ECD) and electron transfer dissociation (ETD) experiments in electrodynamic ion traps operated in the presence of a bath gas in the 1–10 mTorr range have been conducted on a common set of doubly protonated model peptides of the form X(AG)nX (X = lysine, arginine, or histidine, n=1, 2, or 4). The partitioning of reaction products was measured using thermal electrons, anions of azobenzene, and anions of 1,3-dinitrobenzene as reagents. Variation of n alters the charge per residue of the peptide cation, which affects recombination energy. The ECD experiments showed that H-atom loss is greatest for the n=1 peptides and decreases as n increases. Proton transfer in ETD, on the other hand, is expected to increase as charge per residue decreases (i.e., as n increases). These opposing tendencies were apparent in the data for the K(AG)nK peptides. H-atom loss appeared to be more prevalent in ECD than in ETD and is rationalized on the basis of either internal energy differences, differences in angular momentum transfer associated with the electron capture versus electron transfer processes, or a combination of the two. The histidine peptides showed the greatest extent of charge reduction without dissociation, the arginine peptides showed the greatest extent of side-chain cleavages, and the lysine peptides generally showed the greatest extent of partitioning into the c/z•-product ion channels. The fragmentation patterns for the complementary c- and z•-ions for ETD and ECD were found to be remarkably similar, particularly for the peptides with X = lysine.

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“…The square of the impact parameter (in atomic units) takes the form [55]:

b_{E T}^{2} = r_{E T}^{2} [1 + \frac{2 ∣ Z_{cat} Z_{a n} ∣}{r_{E T} μ v_{rel}^{2}}]

Section: Resultsmentioning

confidence: 99%

Cation Recombination Energy/Coulomb Repulsion Effects in ETD/ECD as Revealed by Variation of Charge per Residue at Fixed Total Charge

Mentinova

Crizer

Baba

et al. 2013

J. Am. Soc. Mass Spectrom.

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“…This model postulates the formation of a bound orbit, with a range of eccentricities, for the oppositely charged ions, if the initial relative translational energy from the ionic reactant pair is removed when the reactants are at a critical distance, d orbit . The maximum cross-section for the bound orbit formation (s orbit,max ) has a charge-squared dependence, and is defined as (Mahan, 1973):…”

Section: A Bound Orbit Model To Account For Magnitudes and Z Rate Dementioning

confidence: 99%

“…Studies of this type were complicated by the fact that all of the reaction products are neutral species. Nevertheless, the neutralization kinetics from such reactions have important applications in atmospheric chemistry, combustion studies, and plasmas (Mahan, 1973;Flannery, 1982;Bates, 1985). The development of electrospray ionization (ESI) in the 1980s and early 1990s (Fenn et al, 1989) enabled the formation of multiply charged high-mass gas-phase ions.…”

Section: Introductionmentioning

confidence: 99%

Recent developments in the ion/ion chemistry of high‐mass multiply charged ions

Pitteri

McLuckey

2005

Mass Spectrometry Reviews

155

169

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The ability to form multiply charged high-mass ions in the gas-phase, most notably via electrospray ionization (ESI), has allowed the study of many different combinations of positively and negatively charged ions. The charged products are directly amenable to study with mass spectrometry. Ion/ion reactions have proved to be "universal" in the sense that the high exothermicities and large rate constants associated with essentially any combination of oppositely charged ions lead to reaction regardless of the chemical functionalities associated with the ions. These characteristics make ion/ion reactions potentially analytically useful provided reagent ion densities and spatial overlap of the oppositely charged ions are high. These conditions can be readily met by several instrumental configurations. The focus of this review is to highlight developments in this field since 1998. Novel instrumentation has been developed to study ion/ion reactions, such as atmospheric pressure ion/ion reactors followed by mass analysis, or electrodynamic ion trap mass spectrometers, which are used as reaction vessels at sub-atmospheric pressures. A wide variety of reaction phenomenologies have been observed in various ion/ion reactions, with proton transfer being the most common. New phenomenologies have been observed in the reactions of multiply charged positive ions with singly charged negative ions, including cation transfer and cation exchange. A new series of reactions between multiply charged positive ions and multiply charged negative ions have been made possible by recent instrumentation developments. These reactions have led to the observation of proton transfer and complex formation. These observations have provided new insights into ion/ion reaction dynamics and a bound orbit model appears to best account for experimental results. New applications are also discussed for a several ion/ion reaction.

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“…The square of the impact parameter of each of these interactions (in atomic units) takes the form [58]:…”

Section: Qualitative Trends In Product Partitioningmentioning

confidence: 99%

Gas-phase ion/ion reactions of transition metal complex cations with multiply charged oligodeoxynucleotide anions

Barlow

Hodges

Xia

et al. 2008

J. Am. Soc. Mass Spectrom.

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Multiply deprotonated hexadeoxyadenylate anions, (A 6 ϪnH) nϪ , where n ϭ 3-5, have been subjected to reaction with a range of divalent transition-metal complex cations in the gas phase. The cations studied included the bis-and tris-1,10-phenanthroline complexes of Cu II , Fe II , and Co II , as well as the tris-1,10-phenanthroline complex of Ru II . In addition, the hexadeoxyadenylate anions were subjected to reaction with the singly charged Fe III and Co III N,N=-ethylenebis(salicylideneiminato) complexes. The major competing reaction channels are electron-transfer from the oligodeoxynucleotide anion to the cation, the formation of a complex between the anion and cation, and the incorporation of the transition-metal into the oligodeoxynucleotide. The latter process proceeds via the anion/cation complex and involves displacement of the ligand(s) in the transition-metal complex by the oligodeoxynucleotide. Competition between the various reaction channels is governed by the identity of the transition-metal cation, the coordination environment of the metal complex, and the oligodeoxynucleotide charge state. In the case of the divalent metal phenanthroline complexes, competition between electron-transfer and metal ion incorporation is particularly sensitive to the coordination number of the reagent metal complexes. Both electron-transfer and metal ion incorporation occur to significant extents with the bis-phenanthroline ions, whereas the trisphenanthroline ions react predominantly by metal ion incorporation. To our knowledge this work reports the first observations of the gas-phase incorporation of multivalent transition-metal cations into oligodeoxynucleotide anions and represents a means for the selective incorporation of transition-metal counter-ions into gaseous oligodeoxynucleotides. [6 -8] have allowed the formation of gas-phase ions of biopolymers, including oligodeoxynucleotides (ODNs), making these ions amenable to study by mass spectrometry. Like peptides and proteins, ODNs are amphoteric, [9] allowing formation of either positively or negatively charged ions. Formation of negatively charged oligonucleotides is quite facile using ESI and, as a result, negatively charged ODN ions have been the most widely studied [9]. Oligodeoxynucleotide ions with bound metals formed by MALDI or ESI, especially those containing transition metals, have shown fragmentation behavior, which is distinct and complementary to that of ions devoid of metals [6 -8].The study of the interaction of transition metals with DNA is of critical importance, given the variety of roles such interactions fulfill. Transition-metal complexes display nuclease activity and consequently complexes such as (methidium-propyl-EDTA)iron(II) have been utilized as footprinting agents [10]. Ruthenium(II) complexes have been extensively examined as spectroscopic probes of local DNA structure [11,12]. The mechanism of action of the chemotherapeutic agent cisplatin involves binding to DNA to prevent replication [13][14][15]. Mass spectrometry has been u...

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Recombination of Gaseous Ions

Cited by 59 publications

References 51 publications

Cation Recombination Energy/Coulomb Repulsion Effects in ETD/ECD as Revealed by Variation of Charge per Residue at Fixed Total Charge

Cation Recombination Energy/Coulomb Repulsion Effects in ETD/ECD as Revealed by Variation of Charge per Residue at Fixed Total Charge

Recent developments in the ion/ion chemistry of high‐mass multiply charged ions

Gas-phase ion/ion reactions of transition metal complex cations with multiply charged oligodeoxynucleotide anions

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