Fragmentation of protonated dipeptides containing arginine. Effect of activation method

The fragmentation reactions of the protonated dipeptides Gly-Arg and Arg-Gly have been studied using collision-induced dissociation (CID) in a quadrupole ion trap, by in-source CID in a single-quadrupole mass spectrometer and by CID in the quadrupole cell of a QqTOF mass spectrometer. In agreement with earlier quadrupole ion trap studies (Farrugia, J. M.; O'Hair, R. A. J., Int. J. Mass Spectrom., 2003, 222, 229), the CID mass spectra obtained with the ion trap for the MH(+) ions and major fragment ions are very similar for the two isomers indicating rearrangement to a common structure before fragmentation. In contrast, in-source CID of the MH(+) ions and QqTOF CID of the MH(+), [MH - NH(3)](+) and [MH <23 HN = C(NH(2))(2)](+) ions provide distinctly different spectra for the isomeric dipeptides, indicating that rearrangement to a common structure has not occurred to a significant extent under these conditions even near the threshold for fragmentation in the QqTOF instrument. Clearly, under normal operating conditions significantly different fragmentation behavior is observed in the ion trap and beam-type experiments. This different behavior probably can be attributed to the shorter observation times and concomitant higher excitation energies in the in-source and QqTOF experiments compared to the long observation times and lower excitation energies relevant to the ion trap experiments. Based largely on elemental compositions derived from accurate mass measurements in QqTOF studies fragmentation schemes are proposed for the MH(+), [MH - NH(3)](+), and [MH - (HN = C(NH(2))(2))](+) ions.     

Mass spectra of some new 3,4-dihydro-2[H]-pyridones

Electrospray ionization (ESI) and tandem mass spectrometry (MS/MS) experiments, as well as electronic impact (EI) and chemical ionization (CI) techniques, have been applied to the title compounds 1a-h. The observation of different fragmentation pathways in the three sets of spectra is in accord with different degrees of internal excitation of the investigated precursors. In ESI (methanol as solvent) and CI (methane as reagent gas) spectra, the MH(+) ion represents the most important peak, while the fragments [M - OH](+) and [M - SO](+) are either the base peak or a very abundant peak in the EI mass spectra of these compounds. ESI-MS/MS experiments on the parent ions [MH](+) show that the loss of a fragment of 140 Da corresponding to p-toluenesulfenic acid is common from all the precursors. As well as competitive pathways, the second generation ions have also been elucidated to allow some observations to be made concerning the relationships between structure type and mass spectrometric characteristics.     

Structural assignment of isomeric 2-(2-quinolinyl)-1H-indene-1,3(2H)-dione mono- and disulfonic acids by liquid chromatography electrospray and atmospheric pressure chemical ionization tandem mass spectrometry

Positionally isomeric 2-(2-quinolinyl)-1H-indene-1,3(2H)-dione mono- and disulfonic acids give rise to similar electrospray ionization (ESI) and atmosphere pressure chemical ionization (APCI) mass spectra, which show very abundant MH(+) ions and negligible fragmentation. The MH(+) ions of these isomeric acids exhibit notably different behavior under collision-induced dissociation (CID) conditions. The acids with a sulfonic group at position 8' in the quinoline moiety, adjacent to the N-atom, exhibit highly abundant [MH - H(2)SO(3)](+) ions (m/z 272 for the mono- and m/z 352 for the disulfonic acids), which are of lower abundance in the CID spectra of isomers with the SO(3)H group at other positions, remote from the nitrogen atom. The latter isomers undergo efficient eliminations of SO(3) and HSO(3). The isomeric diacids with one SO(3)H group at position 4 of the indene-1,3(2H)-dione moiety, adjacent to one of the carbonyl groups, undergo highly efficient elimination of H(2)O. Mechanistic pathways, involving interactions between adjacent groups, are proposed for the above regiospecific fragmentations. Pronounced different behavior has been also observed in negative ion tandem mass spectrometric measurements of the sulfonic acids. The distinctive behavior of the isomeric acids was strongly pronounced when the measurements were performed with an ion trap mass spectrometer (LCQ), and much less so with a triple-stage quadrupole instrument (TSQ).     

Peptide sequence scrambling through cyclization of b5 ions

The CID mass spectra of the MH(+) ions and the b(5) ions derived therefrom have been determined for the hexapeptides YAAAAA, AYAAAA, AAYAAA, AAAYAA, and AAAAYA. The CID mass spectra for the b(5) ions derived from the five isomers are essentially identical and show abundant ion signals for nonsequence b ions. This result is consistent with cyclization of the b(5) ions to a cyclic pentapeptide before fragmentation; this cyclic peptide can open at various positions, leading to losses of amino acid residues that are not characteristic of the original amino acid sequence. These nonsequence b ions are also observed in the fragmentation of the MH(+) ions and increase substantially in importance with increasing collision energy. A comparison of the fragmentation of AAAYAA and Ac-AAAYAA indicates that N-acetylation eliminates the cyclization of b(5) ions and, thus, eliminates the nonsequence ions in the CID mass spectra of both b(5) and MH(+) ions.     

The distinction of underivatized monosaccharides using electrospray ionization ion trap mass spectrometry

A convenient method for distinguishing underivatized isomeric monosaccharides has been established using electrospray ionization ion trap mass spectrometry (ESI-ITMS). Mass spectra of hexoses (glucose, galactose, and mannose), N-acetylhexosamines (N-acetylglucosamine, N-acetylgalactosamine, and N-acetylmannosamine) and hexosamines (glucosamine, galactosamine, and mannosamine) dissolved in solvent containing 1 mM ammonium acetate were obtained in the positive ion mode. Glucose was distinguished from galactose and mannose in the MS(2) spectrum of the [M+NH(4)](+) ion at m/z 198. The MS(3) spectra generated from [M+NH(4)-H(2)O-NH(3)](+) at m/z 163 showed that galactose and mannose could be distinguished by the ratio of peak intensities at m/z 145 and 127, while the three N-acetylhexosamine and hexosamine stereochemical isomers could be identified by the relative abundance ratios of product ions observed in MS(3) spectra. The investigation of MS and MS(2) spectra from complexes of these monosaccharides with Na(+) and Pb(2+) failed to distinguish these monosaccharide isomers. Therefore, multiple stage mass analysis by ESI-ITMS using either [M+NH(4)](+) or [M+H](+) was useful to distinguish between the isomers of monosaccharides.     

Dual parallel electrospray ionization and atmospheric pressure chemical ionization mass spectrometry (MS), MS/MS and MS/MS/MS for the analysis of triacylglycerols and triacylglycerol oxidation products

Two mass spectrometers, in parallel, were employed simultaneously for analysis of triacylglycerols in canola oil, for analysis of triolein oxidation products, and for analysis of triacylglycerol positional isomers separated using reversed-phase high-performance liquid chromatography. A triple quadrupole mass spectrometer was interfaced via an atmospheric pressure chemical ionization (APCI) interface to two reversed-phase liquid chromatographic columns in series. An ion trap mass spectrometer was coupled to the same two columns using an electrospray ionization (ESI) interface, with ammonium formate added as electrolyte. Electrospray ionization mass spectrometry (ESI-MS) under these conditions produced abundant ammonium adduct ions from triacylglycerols, which were then fragmented to produce MS/MS spectra and then fragmented further to produce MS/MS/MS spectra. ESI-MS/MS of the ammoniated adduct ions gave product ion mass spectra which were similar to mass spectra obtained by APCI-MS. ESI-MS/MS produced diacylglycerol fragment ions, and additional fragmentation (MS/MS/MS) produced [RCO](+) (acylium) ions, [RCOO+58](+) ions, and other related ions which allowed assignment of individual acyl chain identities. APCI-MS of triacylglycerol oxidation products produced spectra like those reported previously using APCI-MS. APCI-MS/MS produced ions related to individual fatty acid chains. ESI-MS of triacylglycerol oxidation products produced abundant ammonium adduct ions, even for those molecules which previously produced little or no intact molecular ions under APCI-MS conditions. Fragmentation (MS/MS) of the [M+NH(4)](+) ions produced results similar to those obtained by APCI-MS. Further fragmentation (MS/MS/MS) of the diacylglycerol fragments of oxidation products provided information on the oxidized individual fatty acyl chains. ESI-MS and APCI-MS were found to be complementary techniques, which together contributed to a better understanding of the identities of the products formed by oxidation of triacylglycerols.     

Structural determination of hexadecanoic lysophosphatidylcholine regioisomers by fast atom bombardment tandem mass spectrometry

The structural determination of sn-1 and sn-2 hexadecanoic lysophosphatidylcholine (LPC) regioisomers was carried out using fast atom bombardment tandem mass spectrometry (FAB-MS/MS). The collision-induced dissociation (CID) of protonated and sodiated molecules produced diverse product ions due mainly to charge remote fragmentations. Based on the information obtained from the CID spectra of protonated and sodiated molecules, sn-1 and sn-2 hexadecanoic LPC isomers could be discriminated. Especially, the abundance ratio of the diagnostic ion pair [m/z 224/226] in the CID spectra of [M + H](+) ions was shown to be greatly different. Moreover, the CID-MS/MS spectra of sodium-adducted molecules for hexadecanoic LPC isomers showed characteristic product ions such as [M + Na - 103](+), [M + Na - 85](+), and [M + Na - 59](+), by which their regio-specificity can be differentiated.     

Analysis of carrageenans by matrix-assisted laser desorption/ionization and electrospray ionization mass spectrometry. I. kappa-Carrageenans.

Matrix-assisted laser desorption/ionization (MALDI) and electrospray ionization (ESI) mass spectra of small kappa-carrageenans are reported and discussed. MALDI spectra can be obtained in both positive and negative ion mode. In the absence of extraneous metal ions, positive ions are formed by the attachment of one Na(+) ion to the carrageenan, whereas for negative ions one Na(+) ion is detached from the sulfate group. Multiply charged species are not observed in MALDI. Intense ESI spectra can be obtained in negative ion mode and now multiply charged species are seen. Alkali exchange experiments show that in these small carrageenan anions one, but only one, alkali metal ion is bound in a bidentate coordination with two ionic sulfate groups. G2-type ab initio calculations on model ions HO(-) [M(+)] (-)OH (M = Li, Na, K, Cs), as well as arguments based on a simple Coulombic interaction model, show that the bidentate stabilization energy drops rapidly as the size of the alkali cation increases. Exchange of Na(+) with Li(+) leads to expulsion of the Na(+) ion generating, in ESI, intense multiply charged anions. An attempt is made to rationalize this behavior in terms of hydration effects.     

Structural assignment of disialylated biantennary N-glycan isomers derivatized with 2-aminopyridine using negative-ion multistage tandem mass spectral matching

To investigate the possibility of structural assignment based on negative-ion multistage tandem mass (MS(n)) spectral matching, four isomers of disialylated biantennary N-glycans (alpha2-6 and/or alpha2-3 linked sialic acid on alpha1-6 and alpha1-3 antennae) derivatized with 2-aminopyridine (PA) were analyzed by employing high-performance liquid chromatography/electrospray ionization linear ion trap time-of-flight mass spectrometry (HPLC/ESI-LIT-TOFMS), which uses helium gas for ion trapping and collision-induced dissociation (CID). It is shown that the MS(2) spectra derived from each precursor ion [M-2H](2-) are reproducible and useful for distinguishing the four isomers. Thus, they can be assigned by negative-ion MS(2) spectral matching based on correlation coefficients. In addition, MS(3) spectra derived from D-type fragment ions clearly differentiate the alpha2-3- or alpha2-6-linked sialic acid on the alpha1-6 antenna due to their characteristic spectral patterns. The C(4)-type fragment ions, which are produced from both the alpha1-6 and alpha1-3 antennae, show the characteristic MS(3) spectra reflecting alpha2-3- or alpha2-6- linkage type or a mixture of both types. Thus, the differentiation and assignment of these disialylated biantennary N-glycan isomers can also be supported with the MS(3) spectra of C(4)- and D-type ions.     

Collisional activation spectra of [M + Li]+, [M + Na]+ and [M + K]+ ions formed by field desorption of some monosaccharides

The collisional activation spectra of monosaccharide ions formed by [Li]⁺, [Na]⁺ and [K]⁺ ion attachment under field desorption conditions are reported. It is shown that the elimination of the alkali ions is determined by the alkali ion affinities of the molecules (M) and competes with a fragmentation of M which is almost independent of the alkali ion attached. Correspondingly the alkali ion is predominantly retained in the fragment ions. The usefulness of this method for the differentiation of underivatized isomers is demonstrated.     

Structural assignment of isomeric 2-aminopyridine-derivatized monosialylated biantennary N-linked oligosaccharides using negative-ion multistage tandem mass spectral matching

To investigate the possibility of structural assignment based on negative-ion tandem multistage (MSn) mass spectral matching, four isomers of 2-aminopyridine (PA)-derivatized monosialylated oligosaccharides (i.e., complex-type N-glycans with an alpha2-3- or alpha2-6-linked sialic acid on alpha1-6 or alpha1-3 antennae) were analyzed using high-performance liquid chromatography/electrospray ion trap time-of-flight mass spectrometry (HPLC/ESI-IT-TOFMS). The negative ion [M-2H]2- is observed predominantly in the MS1 spectra without the loss of a sialic acid. The MS2 spectra derived from it are sufficiently reproducible that MS2 spectral matching based on correlation coefficients can be applied to the assignment of these isomers. The isomers containing a sialic acid on alpha1-6 or alpha1-3 antennae can be distinguished by MS2 spectral matching, but the alpha2-3 and alpha2-6 linkage types of sialic acid cannot be distinguished by their MS2 spectra. However, MS3 spectra derived from fragment ions containing a sialic acid (i.e., C4- and D-type ions) clearly differentiate the alpha2-3 and alpha2-6 linkage types of sialic acid in their MS3 spectral patterns. This difference might be rationalized in terms of a proton transfer from the reducing-end mannose to the negatively charged sialic acid. These two moieties are very close in the structural conformations of the precursor C4-type fragment ions of alpha2-6 linkage type, as predicted by molecular mechanics calculations. Thus, negative-ion MSn (n = 2, 3) spectral matching was demonstrated to be useful for the structural assignment of these four monosialylated PA N-glycan isomers.     

Tandem mass spectrometry of intact oxidation products of diacylphosphatidylcholines: evidence for the occurrence of the oxidation of the phosphocholine head and differentiation of isomers

Three glycerophosphatidylcholine (GPC) phospholipids (oleoyl-, linoleoyl- and arachidonoylpalmitoylphosphatidylcholine) were oxidized under Fenton reaction conditions (H(2)O(2) and Fe(2+)), and the long-chain oxidation products were detected by electrospray mass spectrometry (ES-MS) and characterized by ES-MS/MS. The intact oxidation products resulted from the insertion of oxygen atoms into the phospholipid structure. The tandem mass spectra of the [MNa](+) molecular ion showed, apart from the characteristic fragments of GPC, fragment ions resulting from neutral losses from [MNa](+), and combined with loss of 59 and 183 Da from [MNa](+). These ions resulted from cleavage of the bond near the hydroxy group by a charge-remote fragmentation mechanism, allowing its location to be pinpointed. The fragments thus formed reflected the positions of the double bonds and of the derivatives along the unsaturated fatty acid chain, giving very useful information, as they allowed the presence of structural isomers and positional isomers to be established. The identification of the fragment ion at m/z 163, which is 16 Da higher than the five-membered cyclophosphane ion (m/z 147), in some tandem mass spectra, is consistent with the oxidation of the phosphocholine head. Some ions were found to occur with the same m/z value; in two of the phospholipids and based on the MS/MS data, structural and positional isomers were differentiated. Our findings indicate that MS/MS is a valuable tool for the identification of the wide complexity of structural features occurring in oxidized phosphatidylcholines during lipid peroxidation in cellular membranes.     

Structural assignment of isomeric 2-aminopyridine-derivatized oligosaccharides using negative-ion MSn spectral matching

To investigate the possibility of structural assignment based on negative-ion MS2 spectral matching, three isomeric pairs of 2-aminopyridine (PA)-derivatized non-fucosylated, fucosylated, and sialylated oligosaccharides (complex type N-glycans) were analyzed using high-performance liquid chromatography/ion trap mass spectrometry (HPLC/ITMS) with a sonic-spray ionization (SSI) source. In the SSI negative-ion mode the deprotonated molecule [M-2H]2- becomes prominent. Negative-ion MS2 spectra derived from such ions contain many fragment types (B and Y, C and Z, A, and D) and therefore are more informative than the positive-ion MS2 spectra derived from [M+H+Na]2+ ions, which usually consist mainly of B and Y fragment ions. In particular the internal ions (D- and E-type ions) provided useful information about the alpha1-6 branching patterns and the bisecting GlcNAc residue. Spectral matching based on the correlation coefficients between negative-ion MS2 spectra was performed in a manner similar to the positive-ion MS2 spectral matching previously reported. It was demonstrated that negative-ion MS2 spectral matching is as useful and applicable to the structural assignment of relatively large non-fucosylated, fucosylated, and sialylated PA-oligosaccharide isomers as its positive-ion counterpart.     

Tandem mass spectra of ammonium ion,metal ion and ligated metal ion adducts of acyclic sugar derivatives

The tandem mass (MS/MS) spectra of ammonium ion, metal ion and ligated metal ion adducts of chain-extended acyclic nitro-containing deoxyglucose and deoxygalactose derivatives have been studied. The ammonium adducts fragment primarily by elimination of ammonia followed by acetic acid, thus not giving much structural information. In contrast, cationization of these compounds by metal ions and ligated metal ions gave structurally informative and useful fragment ions on MS/MS. The metal ions and ligated metal ions play an important role in controlling and directing fragmentation. Retro-aldol fragmentation is facilitated by metal ions such as Li(+), Na(+), Ag(+) and Cu(+), whereas the adducts with higher alkali metal ions such as Rb(+) and Cs(+) fragment to give only the corresponding metal ions. The divalent metal ions such as Cu(2+) and Ba(2+) also induce retro-aldol fragmentation. However, the charge is carried by the aldehyde fragment in the case of Cu(2+) adducts, whereas the nitroalkane fragment carries the charge in the case of Ba(2+) adducts. Ligated metal ions such as ZnCl(+), CuCl(+), InCl(2) (+) and BaCl(+) also behave similarly and induce retro-aldol fragmentation in these acyclic sugars. Both the metal ion and ligated metal ion adducts can fragment by elimination of metal-containing neutral molecules.     

Gas phase ion chemistry of the heterocyclic isomers 3-methyl-1,2-benzisoxazole and 2-methyl-1,3-benzoxazole

Different mass spectrometric methods, stable isotope labeling, and theoretical calculations have allowed us to structurally characterize and differentiate the isomeric ion structures produced by the two heteroaromatic isomers 3-methyl-1,2-benzisoxazole and 2-methyl-1,3-benzoxazole. The low-energy collision induced dissociation spectra of their molecular ions show large differences. Although both of them produce abundant loss of CO, that involves a carbon atom of the benzene ring, the 2-methyl-1,3-benzoxazole also shows abundant [M-CHO](+) ions at m/z 104, the intensity of which is quite low in the case of its isomer 3-methyl-1,2-benzisoxazole. In addition, MS/MS measurements of fragment ions show characteristic differences that allow distinction among the isomers depending on the original arrangement of the atoms in the five-membered ring. Theoretical ab initio calculations have allowed to determine chemico-physical properties of different ions and to propose a rationalization of the decomposition pathways followed by the two benz(is)oxazole isomers.     

Electrospray and atmospheric pressure chemical ionization tandem mass spectrometric behavior of eight anabolic steroid glucuronides

Mass spectrometric and tandem mass spectrometric behavior of eight anabolic steroid glucuronides were examined using electrospray (ESI) and atmospheric pressure chemical ionization (APCI) in negative and positive ion mode. The objective was to elucidate the most suitable ionization method to produce intense structure specific product ions and to examine the possibilities of distinguishing between isomeric steroid glucuronides. The analytes were glucuronide conjugates of testosterone (TG), epitestosterone (ETG), nandrolone (NG), androsterone (AG), 5alpha-estran-3alpha-ol-17-one (5alpha-NG), 5beta-estran-3alpha-ol-17-one (5beta-NG), 17alpha-methyl-5alpha-androstane-3alpha,17beta-diol (5alpha-MTG), and 17alpha-methyl-5beta-androstane-3alpha,17beta-diol (5beta-MTG), the last four being new compounds synthesized with enzyme-assisted method in our laboratory. High proton affinity of the 4-ene-3-one system in the steroid structure favored the formation of protonated molecule [M + H]+ in positive ion mode mass spectrometry (MS), whereas the steroid glucuronides with lower proton affinities were detected mainly as ammonium adducts [M + NH4]+. The only ion produced in negative ion mode mass spectrometry was a very intense and stable deprotonated molecule [M - H]- . Positive ion ESI and APCI MS/MS spectra showed abundant and structure specific product ions [M + H - Glu]+, [M + H - Glu - H2O]+, and [M + H - Glu - 2H2O]+ of protonated molecules and corresponding ions of the ammonium adduct ions. The ratio of the relative abundances of these ions and the stability of the precursor ion provided distinction of 5alpha-NG and 5beta-NG isomers and TG and ETG isomers. Corresponding diagnostic ions were only minor peaks in negative ion MS/MS spectra. It was shown that positive ion ESI MS/MS is the most promising method for further development of LC-MS methods for anabolic steroid glucuronides.     

Fragmentation study of short-chain products derived from oxidation of diacylphosphatidylcholines by electrospray tandem mass spectrometry: identification of novel short-chain products

Lineloyl-palmitoyl (PLPC) and arachidonoyl-palmitoyl (PAPC) phosphatidylcholine were oxidized under Fenton reaction conditions (H2O2 and Fe2+), and the short-chain products formed were identified by electrospray ionization mass spectrometry (ESI-MS). The short-chain products resulted from beta-cleavage of oxygen-centered radicals and comprised aldehydes, hydroxyaldehydes and dicarboxylic acids that yielded both [MH]+ and [MNa]+ ions. The fragmentation of the [MH]+ and [MNa]+ ions of the peroxidation products was studied by tandem mass spectrometry (MS/MS). The MS/MS spectra of both ions showed ions resulting from characteristic losses of glycerophosphatidylcholine. Other product ions, resulting from C-C cleavages occurring in the vicinity of the functional group, and fragmentations involving the hydroxy groups, were the most informative since they allowed us to obtain structural information relating to the sn-2 acyl residue. Both fragmentation pathways are due to charge-remote fragmentation occurring by a 1,4-hydrogen elimination mechanism and/or by homolytic cleavage. Furthermore, the fragmentation pathway of some ions observed in the ESI-MS spectrum was not consistent with the fragmentation behavior expected for some of the short-chain species identified in the literature and allowed the reassignment of the ions as different structures. Isobaric ions were observed in the ESI-MS spectra of both oxidized phospholipids, and were differentiated based on distinct fragmentation. The detailed knowledge of lipid peroxidation degradation products is of major importance and should be very valuable in providing new markers for oxidative stress signaling and for disease states monitoring.     

Structural assignment of isomeric 2-aminopyridine-derivatized oligosaccharides using MSn spectral matching

Two isomeric pairs of 2-aminopyridine (PA)-derivatized fucosylated and non-fucosylated oligosaccharides (complex-type N-glycans of IgG) were analyzed using liquid chromatography/ion trap mass spectrometry (LC/ITMS) with a sonic spray ionization source and by varying the collision-induced dissociation voltage. Reproducibility of MS(n) (n = 2) spectra obtained by LC/ITMS was tested considering both fragment ions (m/z) and intensities. A comparison of their MS(n) spectra and evaluation of similarities (or matching), based on correlation coefficients between MS(n) spectra, was investigated as a possibility for structural assignment of the isomers. It is shown that such MS(n) spectral matching is useful and applicable to the structural assignment of relatively large fucosylated and sialylated PA-oligosaccharides released from IgG based on Bn- and Yn-type fragmentations of the corresponding [M+H+Na](2+) ions.     

Energetics and dynamics of fragmentation of protonated leucine enkephalin from time- and energy-resolved surface-induced dissociation studies

Dissociation of singly protonated leucine enkephalin (YGGFL) was studied using surface-induced dissociation (SID) in a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) specially configured for studying ion activation by collisions with surfaces. The energetics and dynamics of seven primary dissociation channels were deduced from modeling the time- and energy-resolved fragmentation efficiency curves for different fragment ions using an RRKM-based approach developed in our laboratory. The following threshold energies and activation entropies were determined in this study: E(0) = 1.20 eV and DeltaS++ = -20 eu(1) (MH(+)-->b(5)); E(0) = 1.14 eV and DeltaS++ = -14.7 eu (MH(+)-->b(4)); E(0) = 1.42 eV and DeltaS++ = -2.5 eu (MH(+)-->b(3)); E(0) = 1.30 eV and DeltaS++ = -4.1 eu (MH(+)-->a(4)); E(0) = 1.37 eV and DeltaS++ = -5.2 eu (MH(+)-->y ions); E(0) = 1.50 eV and DeltaS++ = 1.6 eu (MH(+)-->internal fragments); E(0) = 1.62 eV and DeltaS++ = 5.2 eu (MH(+)-->F). Comparison with Arrhenius activation energies reported in the literature demonstrated for the first time the reversal of the order of activation energies as compared to threshold energies for dissociation.     

Effect of alkali metal coordination on gas-phase chemistry of the diphosphate ion: the MH(2)P(2)O(7) (-) ions

Systematic experimental and theoretical studies on anionic phosphate species in the gas phase are almost nonexistent, even though they could provide a benchmark for enhanced comprehension of their liquid-phase chemical behavior. Gaseous MH(2)P(2)O(7) (-) ions (M=Li, Na, K, Rb, Cs), obtained from electrospray ionization of solutions containing H(4)P(2)O(7) and MOH or M salts as a source of M(+) ions were structurally assayed by collisionally activated dissociation (CAD) mass spectrometry and theoretical calculations at the B3LYP/6-31+G* level of theory. The joint application of mass spectrometric techniques and theoretical methods allowed the MH(2)P(2)O(7) (-) ions to be identified as having a structure in which the linear diphosphate anion is coordinated to the M(+) ion (I) and provides information on gas-phase isomerization processes in the [PO(3)...MH(2)PO(4)](-) clusters II and the [P(2)O(6)...M...H(2)O](-) clusters IV. Studies of gas-phase reactivity by Fourier transform ion cyclotron resonance (FTICR) and triple quadrupole (TQ) mass spectrometry revealed that the MH(2)P(2)O(7) (-) ions react with selected nucleophiles by clustering, proton transfer and addition-elimination mechanisms. The influence of the coordination of alkali metal ions on the chemical behavior of pyrophosphate is discussed.