Products Of Ion-molecule Reactions Research Articles

Chemical Synthesis with Gaseous Molecular Ions: Harvesting [B12 Br11 N2 ]- from a Mass Spectrometer.

Mass spectrometry frequently reveals the existence of transient gas phase ions that have not been synthesized in solution or in bulk. These elusive ions are, therefore, often considered to be primarily of analytical value in fundamental gas phase studies. Here, we provide proof-of-concept that the products of ion-molecule reactions in mass spectrometers may be collected on surfaces to generate condensed matter and thus serve as building blocks to synthesize new compounds. The highly reactive fragment anion [B12 Br11 ]- was generated in a mass spectrometer and converted to [B12 Br11 N2 ]- in the presence of molecular nitrogen followed by its mass-selection and soft-landing on surfaces. The molecular structure of [B12 Br11 N2 ]- , which has not been synthetically obtained before, was confirmed by conventional methods of molecular analysis, including nuclear magnetic resonance and infrared spectroscopy. The [B12 Br11 N2 ]- ion is stable on surfaces and in solution at room temperature, but thermal annealing induces elimination of N2 and provides access to the highly reactive intermediate [B12 Br11 ]- in the condensed phase, which can be further used as a reagent, for example, for electrophilic aromatic substitutions. Thus, isolation of [B12 Br11 N2 ]- expands the repertoire of the available diazo ions that can be employed as versatile intermediates in various chemical transformations.

Differentiation of the Aziridine Functionality from Related Functional Groups in Protonated Analytes by Using Selective Ion-Molecule Reactions Followed by Collision-Activated Dissociation in a Linear Quadrupole Ion Trap Mass Spectrometer.

Aziridines are commonly used as reagents for the synthesis of drug substances although they are potentially mutagenic and genotoxic. Therefore, their unambiguous detection is critically important. Unfortunately, tandem mass spectrometry (MS2) based on collision-activated dissociation (CAD), a powerful method used for the identification of many unknown compounds in complex mixtures, does not provide diagnostic fragmentation patterns for ionized aziridines. Therefore, a different mass spectrometry approach based on MS3 experiments is presented here for the identification of the aziridine functionalities. This approach is based on selective gas-phase ion-molecule reactions of protonated analytes with tris(dimethylamino)borane (TDMAB) followed by diagnostic CAD reactions in a modified linear quadrupole ion trap (LQIT) mass spectrometer. TDMAB reacts with protonated aziridines by forming adduct ions that have lost a dimethylamine (DMA) molecule ([M + H + TDMAB - HN(CH3)2]+). CAD on these product ions generated diagnostic fragment ions with m/z-values 25- and 43-units lower than those of the ion-molecule reaction product ions. None of the ion-molecule reaction product ions formed from other, structurally related, protonated analytes produced related fragment ions. Quantum chemical calculations were employed to explore the mechanisms of the observed reactions.

Monitoring the Light-induced Isomerisation of the Prototypical Polycyclic Aromatic Hydrocarbons C10 H8 + through Ion-Molecule Reactions.

Structural rearrangements in ions are essential for understanding the composition and evolution of energetic and chemically active environments. This study explores the interconversion routes for simple polycyclic aromatic hydrocarbons, namely naphthalene and azulene radical cations (C10 H8 + ), by combining mass spectrometry and vacuum ultraviolet tunable synchrotron radiation through the chemical monitoring technique. Products of ion-molecule reactions are used to probe C10 H8 + structures that are formed as a function of their internal energies. Isomerisation from azulene radical cation towards naphthalene radical cation in a timescale faster than 80 μs was monitored, whereas no reverse isomerisation was observed in the same time window. When energising C10 H8 + with more than 6 eV, the reactivity of C10 H8 + unveils the formation of a new isomeric group with a contrasted reactivity compared with naphthalene and azulene cations. We tentatively assigned these structures to phenylvinylacetylene cations.

Differentiation of Protonated Sulfonate Esters from Isomeric Sulfite Esters and Sulfones by Gas-Phase Ion-Molecule Reactions Followed by Diagnostic Collision-Activated Dissociation in Tandem Mass Spectrometry Experiments.

Sulfonate esters, a class of potentially mutagenic drug impurities, are strictly regulated in pharmaceuticals. On the other hand, sulfite esters and sulfones, analogs of sulfonate esters, have limited safety concerns. However, previously developed analytical methods for sulfonate ester identification cannot be used to differentiate sulfonate esters from the isomeric sulfite esters and sulfones. A tandem mass spectrometric method is introduced here for the differentiation of these compounds. Diisopropoxymethylborane (DIMB) reacts with protonated sulfonate esters, sulfite esters, and sulfones (and many other compounds) in the gas phase to form the product ion [M + H + DIMB - CH3CH(OH)CH3]+. Upon collision-activated dissociation (CAD), these product ions generate diagnostic fragment ions that enable the differentiation of sulfonate esters, sulfite esters, and sulfones from each other. For example, SO2 elimination enabled the unambiguous identification of sulfite esters. On the other hand, elimination of CH3B═O followed by elimination of (CH3)2C═O was only observed for sulfonate esters. Neither type of diagnostic fragment ions was detected for the products of sulfones. However, the product ions formed for sulfones with an additional hydroxyl substituent underwent the elimination of another CH3CH(OH)CH3 molecule, which enabled their identification. Finally, ion-molecule reactions of DIMB with various other functionalities were also examined. Some of them yielded the product ions [M + H + DIMB - CH3CH(OH)CH3]+ but none of these product ions underwent the diagnostic CAD reactions discussed above. Quantum chemical calculations were employed to explore the mechanisms of the reactions. The limits of detection for the diagnostic ion-molecule reaction product ions in high-performance liquid chromatography (HPLC)/mass spectrometry (MS2) experiments were found to range from 0.075 to 1.25 nmol.

Characterization of Protonated Substituted Ureas by Using Diagnostic Gas-Phase Ion-Molecule Reactions Followed by Collision-Activated Dissociation in Tandem Mass Spectrometry Experiments.

Substituted ureas correspond to a class of organic compounds commonly used in agricultural and chemical fields. However, distinguishing between different ureas and differentiating substituted ureas from other compounds with similar structures, such as amides, N-oxides, and carbamates, are challenging. In this paper, a four-stage tandem mass spectrometry method (MS4) is introduced for this purpose. This method is based on gas-phase ion-molecule reactions of isolated, protonated analytes ([M + H]+) with tris(dimethylamino)borane (TDMAB) (MS2) followed by subjecting a diagnostic product ion to two steps of collision-activated dissociation (CAD) (MS3 and MS4). All the analyte ions reacted with TDMAB to form a product ion [M + H + TDMAB - HN(CH3)2]+. The product ion formed for substituted ureas and amides eliminated another HN(CH3)2 molecule upon CAD to generate a fragment ion [M + H + TDMAB - 2HN(CH3)2]+, which was not observed for many other analytes, such as N-oxides, sulfoxides, and pyridines (studied previously). When the [M + H + TDMAB - 2HN(CH3)2]+ fragment ion was subjected to CAD, different fragment ions were generated for ureas, amides, and carbamates. Fragment ions diagnostic for the ureas were formed via elimination of R-N═C═O (R = hydrogen atom or a substituent), which enabled the differentiation of ureas from amides and carbamates. Furthermore, these fragment ions can be utilized to classify differently substituted ureas. Quantum chemical calculations were employed to explore the mechanisms of the reactions. The limit of detection for the diagnostic ion-molecule reaction product ion in HPLC/MS2 experiments was found to range from 20 to 100 nM.

In-tube collision-induced dissociation for selected ion flow-drift tube mass spectrometry, SIFDT-MS: a case study of NO(+) reactions with isomeric monoterpenes.

Soft chemical ionisation techniques including selected ion flow tube mass spectrometry, SIFT-MS, and proton transfer reaction mass spectrometry, PTR-MS, cannot currently quantify individual isomers present simultaneously in samples, a notable example being atmospheric monoterpenes. A possible solution lies in integrating in-tube collision-induced dissociation, CID, into a selected ion flow-drift tube mass spectrometry, SIFDT-MS, instrument. In-tube CID was implemented by applying electrostatic potential difference between the resistive glass flow-drift tube downstream end and the nose cone of a quadrupole mass spectrometer. The resulting inhomogeneous electric field accelerates the product ions along the last 1mm before the nose cone and causes their dissociation in collisions with molecules of the buffer gas (4% air, 96% helium, 2mbar). Mass spectra of the product ions of NO(+) reactions with 3-carene, β-pinene, (S)-limonene and their mixture were obtained for variable potential difference. Potential difference up to 47.7V resulted in dramatic changes in the mass spectra due to fragmentation of the monoterpene radical molecular cations. The main observed fragments correspond to logical losses from different isomeric structures. Fragmentation increases with the potential difference and can be interpreted as single collision dissociation on air molecules at centre-of-mass energies of several eV. Combination of fragmentation patterns at different CID enables distinction of isomers in the mixture on the basis of pseudoinversion. In-tube CID represents a simple and low-cost extension to SIFDT-MS that allows real-time identification of isomeric products of ion-molecule reactions on the basis of their structural differences and corresponding changes in fragmentation patterns with CID energy without significantly changing the net reaction time important for absolute quantification. Copyright © 2016 John Wiley & Sons, Ltd.

Identification of 2-aminothiazolobenzazepine metabolites in human, rat, dog, and monkey microsomes by ion-molecule reactions in linear quadrupole ion trap mass spectrometry.

2-Aminothiazolobenzazepine (2-ATBA), 7-[(1-methyl-1H-pyrazol-4-yl)methyl]-6,7,8,9-tetrahydro-5H-[1,3]thiazolo[4,5-h][3]benzazepin-2-amine, is a D2 partial agonist that has demonstrated antipsychotic effects in a rodent in vivo efficacy model. The metabolite profile showed that 2-ATBA is mainly metabolized by oxidation. However, identification of the oxidation site(s) in the 2-aminothiazole group presents a challenge for the traditional metabolite identification methods such as liquid chromatography/mass spectrometry and NMR due to the lack of unique tandem mass spectrometry fragmentation patterns for ions with the 2-aminothiazole group oxidized at different sites and the lack of stability for purification or reference standard synthesis. We describe the characterization of the oxidized heteroatoms of the 2-aminothiazole group via gas-phase ion-molecule reactions (GPIMR) in a modified linear quadrupole ion trap mass spectrometer. The GPIMR reagents used were dimethyl disulfide, tert-butyl peroxide, and tri(dimethylamino)borane. Each reagent was introduced into the ion trap through the helium line and was allowed to react with the protonated metabolites. The ionic ion-molecule reaction products and their fragmentation profiles were compared with the profiles of the ionic ion-molecule reaction products of protonated reference compounds that had specific heteroatom functionalities. The oxidized 2-aminothiazole metabolite of 2-ATBA showed a similar GPIMR profile to that of the reference compounds with a tertiary N-oxide functionality and distinct from the profiles of the reference compounds with N-aryl hydroxylamine, nitroso, or pyridine N-oxide functionalities. This study demonstrates the feasibility of fingerprinting the chemical nature of oxidized nitrogen functional groups via GPIMR profiling for metabolite structure elucidation.

Differentiation of Protonated Aromatic Regioisomers Related to Lignin by Reactions with Trimethylborate in a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer

Several lignin model compounds were examined to test whether gas-phase ion-molecule reactions of trimethylborate (TMB) in a FTICR can be used to differentiate the ortho-, meta-, and para-isomers of protonated aromatic compounds, such as those formed during degradation of lignin. All three regioisomers could be differentiated for methoxyphenols and hydroxyphenols. However, only the differentiation of the ortho-isomer from the meta- and para-isomers was possible for hydroxyacetophenones and hydroxybenzoic acids. Consideration of the previously reported proton affinities at all basic sites in the isomeric hydroxyphenols, and the calculated proton affinities at all basic sites in the three methoxyphenol isomers, revealed that the proton affinities of the analytes relative to that of TMB play an important role in determining whether and how they react with TMB. The loss of two methanol molecules (instead of one) from the adducts formed with TMB either during ion-molecule reactions, or during sustained-off resonance irradiated collision-activated dissociation of the ion-molecule reaction products, revealed the presence of two functionalities in almost all the isomers. This finding supports earlier results suggesting that TMB can be used to count the functionalities in unknown oxygen-containing analytes.

Differentiation of Regioisomeric Aromatic Ketocarboxylic Acids by Positive Mode Atmospheric Pressure Chemical Ionization Collision-Activated Dissociation Tandem Mass Spectrometry in a Linear Quadrupole Ion Trap Mass Spectrometer

Positive-mode atmospheric pressure chemical ionization tandem mass spectrometry (APCI-MS(n)) was tested for the differentiation of regioisomeric aromatic ketocarboxylic acids. Each analyte forms exclusively an abundant protonated molecule upon ionization via positive-mode APCI in a commercial linear quadrupole ion trap (LQIT) mass spectrometer. Energy-resolved collision-activated dissociation (CAD) experiments carried out on the protonated analytes revealed fragmentation patterns that varied based on the location of the functional groups. Unambiguous differentiation between the regioisomers was achieved in each case by observing different fragmentation patterns, different relative abundances of ion-molecule reaction products, or different relative abundances of fragment ions formed at different collision energies. The mechanisms of some of the reactions were examined by H/D exchange reactions and molecular orbital calculations.

Experimental Determination of Energy Disposal in the Dissociative Electron Recombinations of CS2+ and HCS2+

Vibronic optical emissions from CS(A1pi --> X1sigma+) and CS(a3pi --> X1sigma+) transitions have been identified from dissociative recombination (DR) of CS2(+) and HCS2(+) plasmas. All of the spectra were taken in flowing afterglow plasmas using an optical monochromator in the UV-visible wavelength region of 180-800 nm. For the CS(A --> X) and CS(a --> X) emissions, the relative vibrational distributions have been calculated for v' < 5 and v' < 3 in both types of plasmas for the CS(A) and CS(a) states, respectively. Both recombining plasmas show a population inversion from the v' = 0 to v' = 1 level of the CS(A) state, similar to other observations of the CS(A) state populations, which were generated using two other energetic processes. The possibility of spectroscopic cascading is addressed, such that transitions from upper level electronic states into the CS(A) and CS(a) states would affect the relative vibrational distribution, and there is no spectroscopic evidence supporting the cascading effect. Additionally, excited-state transitions from neutral sulfur (S(5S(2)0 --> 3P(2)) and S(5S(2)0 --> 3P(1))) and the products of ion-molecule reactions (CS(B1sigma+ --> A1pi), CS(+)(B2sigma+ --> A2pi(i)), and CS2(+) (A2pi(u) --> X2pi(g))) have been observed and are discussed.

Sugar Synthesis from a Gas-Phase Formose Reaction

Prebiotic possibilities for the synthesis of interstellar ribose through a protic variant of the formose reaction under gas-phase conditions were studied in the absence of any known catalyst. The ion-molecule reaction products, diose and triose, were sought by mass spectrometry, and relevant masses were observed. Ab initio calculations were used to evaluate protic formose mechanism possibilities. A bilateral theoretical and experimental effort yielded a physical model for glycoaldehyde generation whereby a hydronium cation can mediate formaldehyde dimerization followed by covalent bond formation leading to diose and water. These results advance the possibility that ion-molecule reactions between formaldehyde (CH(2)O) and H(3)O(+) lead to formose reaction products and inform us about potential sugar formation processes in interstellar space.

A thermal extrapolation method for the effective temperatures and internal energies of activated ions

The internal energies of dissociating ions, activated chemically or collisionally, can be estimated using the kinetics of thermal dissociation. The thermal Arrhenius parameters can be combined with the observed dissociation rate of the activated ions using k diss = A thermalexp(− E a,thermal/ RT eff). This Arrhenius-type relation yields the effective temperature, T eff, at which the ions would dissociate thermally at the same rate, or yield the same product distributions, as the activated ions. In turn, T eff is used to calculate the internal energy of the ions and the energy deposited by the activation process. The method yields an energy deposition efficiency of 10% for a chemical ionization proton transfer reaction and 8–26% for the surface collisions of various peptide ions. Internal energies of ions activated by chemical ionization or by gas phase collisions, and of ions produced by desorption methods such as fast atom bombardment, can be also evaluated. Thermal extrapolation is especially useful for ion–molecule reaction products and for biological ions, where other methods to evaluate internal energies are laborious or unavailable.

Isomeric Effects in the Gas-Phase Reactions of Dichloroethene, C2H2Cl2, with a Series of Cations

A study of the reactions of a series of gas-phase cations (NH(4)(+), H(3)O(+), SF(3)(+), CF(3)(+), CF(+), SF(5)(+), SF(2)(+), SF(+), CF(2)(+), SF(4)(+), O(2)(+), Xe(+), N(2)O(+), CO(2)(+), Kr(+), CO(+), N(+), N(2)(+), Ar(+), F(+), and Ne(+)) with the three structural isomers of dichloroethene, i.e., 1,1-C(2)H(2)Cl(2), cis-1,2-C(2)H(2)Cl(2), and trans-1,2-C(2)H(2)Cl(2) is reported. The recombination energy (RE) of these ions spans the range of 4.7-21.6 eV. Reaction rate coefficients and product branching ratios have been measured at 298 K in a selected ion flow tube (SIFT). Collisional rate coefficients are calculated by modified average dipole orientation (MADO) theory and compared with experimental data. Thermochemistry and mass balance have been used to predict the most feasible neutral products. Threshold photoelectron-photoion coincidence spectra have also been obtained for the three isomers of C(2)H(2)Cl(2) with photon energies in the range of 10-23 eV. The fragment ion branching ratios have been compared with those of the flow tube study to determine the importance of long-range charge transfer. A strong influence of the isomeric structure of dichloroethene on the products of ion-molecule reactions has been observed for H(3)O(+), CF(3)(+), and CF(+). For 1,1-C(2)H(2)Cl(2) the reaction with H(3)O(+) proceeds at the collisional rate with the only ionic product being 1,1-C(2)H(2)Cl(2)H(+). However, the same reaction yields two more ionic products in the case of cis-1,2- and trans-1,2-C(2)H(2)Cl(2), but only proceeds with 14% and 18% efficiency, respectively. The CF(3)(+) reaction proceeds with 56-80% efficiency, the only ionic product for 1,1-C(2)H(2)Cl(2) being C(2)H(2)Cl(+) formed via Cl(-) abstraction, whereas the only ionic product for both 1,2-isomers is CHCl(2)(+) corresponding to a breaking of the C=C double bond. Less profound isomeric effects, but still resulting in different products for 1,1- and 1,2-C(2)H(2)Cl(2) isomers, have been found in the reactions of SF(+), CO(2)(+), CO(+), N(2)(+), and Ar(+). Although these five ions have REs above the ionization energy (IE) of any of the C(2)H(2)Cl(2) isomers, and hence the threshold for long-range charge transfer, the results suggest that the formation of a collision complex at short range between these ions and C(2)H(2)Cl(2) is responsible for the observed effects.

Gas-phase bimolecular reactions between (.)CH(2)-(CH(2))(n)-C(+)=O distonic ions and pyridine: a combined experimental and theoretical study.

The gas-phase reactivities of the well-known (.)CH(2)CH(2)C(+)=O and (.)CH(2)CH(2)CH(2)C(+)=O distonic ions towards neutral pyridine were studied both experimentally (six sector hybrid mass spectrometer) and theoretically (density functional theory and Møller-Plesset ab initio calculations). Competitively to the charge exchange and protonation processes, both radical cations react with pyridine by an initial bonding between the positive charge site of the ion and the lone electron pair of the neutral molecule. At variance with previously reported studies in which such a nucleophilic interaction was proposed to play only a transient catalytic role, the initial C-N bond is likely to remain in the observed ion-molecule reaction products. The structures of the ion-molecule reactions products were probed by collisional activation at high kinetic energy and the reaction pathways were tentatively proposed on the basis of labeling experiments and ab initio molecular orbital calculations.

Taming halonium metathesis

The halonium metathesis reaction of ketones and aldehydes,  C O+ XF +→ C F ++ X O is difficult to harness for three reasons: (1) the interchange of F + for O is so exothermic that the CF + product ion often decomposes further; (2) the adduct of XF + to the carbonyl oxygen frequently undergoes side reactions to the virtual exclusion of metathesis; and (3) the metathesis ion is liable to rearrange to a mixture of isomers. Several approaches have been explored to make this reaction a useful source of gaseous fluoroalkyl cations. DFT calculations reinforce the intuition that cyclopentenone should give a good yield of metathesis ions in its ion–molecule reaction with CF 3 +, an expectation that is borne out by experiment. Other approaches have met with less dramatic success. Variation of XF + gives a number of interesting results, but little improvement over CF 3 +. Deuterium substitution at the carbon adjacent to the carbonyl (α-position) does not restrain further decomposition, but deuteration of the next carbon (β-position) does appear to do so. The isotopic labeling experiments indicate that the prevalent mode of decomposition requires hydrogen shift followed by a 1,3-elimination of HF. Observed side reactions of adduct ions include alkene expulsion to yield CF 3-containing products (such as m/ z 125 from the reaction of cycloalkanones with CF 3 +) and direct elimination of HF (as conjectured for the reaction of CFO + with diethyl ketone, with concurrent loss of CO 2). Structures of ion–molecule reaction products can be reliably inferred only when the expected mechanism yields the minimum energy structure for that molecular formula.

Gas-phase halonium metathesis and its competitors. Skeletal rearrangements of cationic adducts of saturated ketones.

The methyl cation and CF(3)(+) attack saturated, acyclic ketones to make vibrationally excited adduct ions. Despite their high internal energies and short lifetimes, these adducts undergo deep-seated rearrangements that parallel slower processes in solution. Observed pathways include alkene and alkane expulsions, in addition to (in the case of CF(3)(+)) the precedented loss of CF(2)O + HF. For the vast majority of ketones, the principal charged products are the CF(3)(+) adducts of lighter carbonyl compounds, ions that are not easily prepared by other avenues. Evidence for ion structures comes from collisionally activated unimolecular decomposition and bimolecular ion-molecule reactions. Typical examples are di-n-propyl and diisopropyl ketones (both of which produce CH(3)CH=OCF(3)(+) as the principal ion-molecule reaction product) and pentamethylacetone (which produces (CH(3))(2)C=OCF(3)(+) as virtually the sole ion-molecule reaction product). Isotopic labeling experiments account for mechanisms, and DFT calculations provide a qualitative explanation for the relative abundances of products from unimolecular decompositions of the chemically activated CF(3)(+) adduct ions that are initially formed.

Multiple stage pentaquadrupole mass spectrometry for generation and characterization of gas-phase ionic species. The case of the PyC 2H 5+· isomers

Eleven isomers with the PyC2H 5 (+·) composition, which include three conventional (1-3) and eight distonic radical cations (4-11), have been generated and in most cases successfully characterized in the gas phase via tandem-in-space multiple-stage pentaquadrupole MS(2) and MS(3) experiments. The three conventional radical cations, that is, the ionized ethylpyridines C2H5-C5H4N(+·) (1-3), were generated via direct 70-eV electron ionization of the neutrals, whereas sequences of chemical ionization and collision-induced dissociation (CID) or mass-selected ion-molecule reactions were used to generate the distonic ions H2C(·)-C5H4N(+)-CH3 (4-6), CH3-C5H4N(+)-CH 2 (·) (7-9), C5H5N(+)-CH2CH 2 (·) (10), and C5H5N(+)-CH(·)-CH3 (11). Unique features of the low-energy (15-eV) CID and ion-molecule reaction chemistry with the diradical oxygen molecule of the isomers were used for their structural characterization. All the ion-molecule reaction products of a mass-selected ion, each associated with its corresponding CID fragments, were collected in a single three-dimensional mass spectrum. Ab initio calculations at the ROMP2/6-31G(d, p)//6-31G(d, p)+ZPE level of theory were performed to estimate the energetics involved in interconversions within the PyC2H5 (+·) system, which provided theoretical support for facile 4⇌7 interconversion evidenced in both CID and ion-molecule reaction experiments. The ab initio spin densities for the a-distonic ions 4-9 and 11 were found to be largely on the methylene or methyne formal radical sites, which thus ruled out substantial odd-spin derealization throughout the neighboring pyridine ring. However, only 8 and 9 (and 10) react extensively with oxygen by radical coupling, hence high spin densities on the radical site of the distonic ions do not necessarily lead to radical coupling reaction with oxygen. The very typical "spatially separated" ab initio charge and spin densities of 4-11 were used to classify them as distonic ions, whereas 1-3 show, as expected, "localized" electronic structures characteristic of conventional radical ions.

Cation attachment to multiply charged anions of oxidized bovine insulin A-chain.

Multiply charged anions of oxidized bovine insulin A-chain react with protonated quinoline exclusively by proton transfer in a Paul trap operated with helium bath gas at a pressure of 10(-3) Torr. The isomeric [C9H8N]+ ions formed from the reaction of [C4H4]+ with pyridine, on the other hand, react largely by attachment to the multiply charged anions of oxidized bovine insulin A-chain. This observation can be rationalized on the basis of competition between unimolecular decomposition versus cooling of the ion-ion collision complex. In the case of protonated quinoline, no significant barriers are expected along the reaction coordinate for proton transfer. However, the [C9H8N]+ ion-molecule reaction product is not expected to transfer a proton without undergoing rearrangement, as is consistent with ion trap collisional activation results. The rearrangement reaction introduces a significant barrier along the reaction coordinate, thereby increasing the lifetime of the ion-ion collision complex. RRKM modeling for a polypeptide of comparable size suggests that a barrier of 0.6 eV or greater will allow for the observation of cation attachment whereas the lifetimes of collision complexes with well depths less than approximately 0.6 eV are too short for collisional cooling by the bath gas to be effective.

Guided ion beam measurement of the product branching ratios for the ion-molecule reaction N++O2 as a function of collision energy

A quadrupole-octopole-quadrupole mass spectrometer has been constructed for comparing ion-molecule reaction product intensities as both the internal excitation and the kinetic energy of the reactant ion are varied. Such comparisons require an ion beam with a known kinetic energy distribution and, most importantly, they require product intensity measurements made without significant bias in detection of the different product channels. To assess the characteristics of our instrument, we have studied the ion-molecule reaction N++O2 that is known to yield three different product channels: N+O+2, NO++O, and NO+O+. Ion beam trajectory simulations combined with experimental measurements show that the spread in the kinetic energy of the reagent ions has a fixed value in the range of 0.6 to 1.1 eV full width at half maximum in the center of mass (c.m.). Relative cross sections for the three different product channels are reported as a function of c.m. collision energy. A comparison of the observed product branching ratios with those determined previously by other workers shows that no serious product discrimination occurs over the collision energy range of 1.5 to 10.0 eV c.m. Discrepancies in the product branching ratios below 1.5 eV c.m. are believed to be caused by the overall collision energy uncertainty that results from both the ion beam kinetic energy spread and the thermal motion of the O2 reactant.

Multiple stage mass spectrometry: the next generation tandem mass spectrometry experiment

Tandem mass spectrometry has become a powerful tool for basic and applied mass spectrometry studies. Mass spectrometers based on ion trapping techniques, such as the quadrupole ion trap, have some unique capabilities as tandem mass spectrometers. Of particular note are the high MS–MS efficiency, the ability to perform multiple stages of tandem spectrometry (MSn), and the ability to effect ion–molecule reactions as part of the experimental sequence. This paper discusses the MSn experiment in a quadrupole ion trap and provides several examples of MSn experiments in which ion–molecule reactions are incorporated as one or more steps in the experiment. Examples include one in which MSn is used to determine the structure of an ion–molecule reaction product, one that involves multiple stages of collision-induced dissociation to generate a 13C containing reactant ion for an isotopic study, and one in which ion–molecule reactions are used to differentiate isomeric ion structures.