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Electrospray ionization and multiple-stage tandem mass spectrometry were used to study the collision-induced dissociation of methanol-coordinated copper-acetate cations, and the ion-molecule reactions of specific product ions. Our experiments led to the discovery of unusual gas-phase ions with compositions such as [Cu(CO2)(CH3OH)]+ and [Cu(N2)(CH3OH)]+. The latter is generated by spontaneous exchange of CO2 for N2 in an ion-molecule reaction. Isotopic labeling studies and high mass-resolution measurements provide data to support the product ion composition assignments. Density functional theory calculations corroborate the experimental observations, both with respect to the preferential decarboxylation over methanol ligand elimination, and the spontaneous nature of the ion-molecule reactions.

Electrospray ionization was used to generate species such as [ZnNO3(CH3OH)2]+ from Zn(NO3)2•XH2O dissolved in a mixture of CH3OH and H2O. Collision-induced dissociation of [ZnNO3(CH3OH)2]+ causes elimination of CH3OH to form [ZnNO3(CH3OH)]+. Subsequent collision-induced dissociation of [ZnNO3(CH3OH)]+ causes elimination of 47 mass units (u), consistent with ejection of HNO2. The neutral loss shifts to 48 u for collision-induced dissociation of [ZnNO3(CD3OH)]+, demonstrating the ejection of HNO2 involves intra-complex transfer of H from the methyl group methanol ligand. Subsequent collision-induced dissociation causes the elimination of 30 u (32 u for the complex with CD3OH), suggesting the elimination of formaldehyde (CH2 = O). The product ion is [ZnOH]+. Collision-induced dissociation of a precursor complex created using CH3-18OH shows the isotope label is retained in CH2 = O. Density functional theory calculations suggested that the “rearranged” product, ZnOH with bound HNO2 and formaldehyde is significantly lower in energy than ZnNO3 with bound methanol. We therefore used infrared multiple-photon photodissociation spectroscopy to determine the structures of both [ZnNO3(CH3OH)2]+ and [ZnNO3(CH3OH)]+. The infrared spectra clearly show that both ions contain intact nitrate and methanol ligands, which suggests that rearrangement occurs during collision-induced dissociation of [ZnNO3(CH3OH)]+. Based on the density functional theory calculations, we propose that transfer of H, from the methyl group of the CH3OH ligand to nitrate, occurs in concert with the formation of a Zn–C bond. After dissociation to release HNO2, the product rearranges with the insertion of the remaining O atom into the Zn–C bond. Subsequent C–O bond cleavage, with H transfer, produces an ion–molecule complex composed of [ZnOH]+ and O = CH2.

Uranium trioxide, UO

Uranium trioxide, UO3, has a T-shaped structure with bent uranyl, UO22+, coordinated by an equatorial oxo, O2-. The structure of cation UO3+ is similar but with an equatorial oxyl, O center dot-. Neutral and cationic uranium trioxide coordinated by nitrates were characterized by collision induced dissociation (CID), infrared multiple-photon dissociation (IRMPD) spectroscopy, and density functional theory. CID of uranyl nitrate, [UO2 (NO3)3]- (complex A1), eliminates NO2 to produce nitrate-coordinated UO3+, [UO2 (O. )(NO3)2]-(B1), which ejects NO3 to yield UO3 in [UO2 (O)(NO3)]- (C1). Finally, C1 associates with H2O to afford uranyl hydroxide in [UO2(OH)2 (NO3)]- (D1). IRMPD of B1, C1, and D1 confirms uranyl equatorially coordinated by nitrate(s) along with the following ligands: (B1) radical oxyl O.-; (C1) oxo O2-; and (D1) two hydroxyls, OH- . As the nitrates are bidentate, the equatorial coordination is six in A1, five in B1, four in D1, and three in C1. Ligand congestion in low-coordinate C1 suggests orbital-directed bonding. Hydrolysis of the equatorial oxo in C1 epitomizes the inverse trans influence in UO3, which is uranyl with inert axial oxos and a reactive equatorial oxo. The uranyl v3 IR frequencies indicate the following donor ordering: O2- [best donor] >> O.- > OH-> NO3-.

Bupropion is an atypical antidepressant and smoking cessation aid associated with wide intersubject variability. This study compared the formation kinetics of three phase I metabolites (hydroxybupropion, threohydrobupropion, and erythrohydrobupropion) in human, marmoset, rat, and mouse liver microsomes. The objective was to establish suitability and limitations for subsequent use of nonclinical species to model bupropion central nervous system (CNS) disposition in humans. Hepatic microsomal incubations were conducted separately for the R- and S-bupropion enantiomers, and the formation of enantiomer-specific metabolites was determined using LC-MS/MS. Intrinsic formation clearance (CLint) of metabolites across the four species was determined from the formation rate versus substrate concentration relationship. The total clearance of S-bupropion was higher than that of R-bupropion in monkey and human liver microsomes. The contribution of hydroxybupropion to the total racemic bupropion clearance was 38%, 62%, 17%, and 96% in human, monkey, rat, and mouse, respectively. In the same species order, threohydrobupropion contributed 53%, 23%, 17%, and 3%, and erythrohydrobupropion contributed 9%, 14%, 66%, and 1.3%, respectively, to racemic bupropion clearance. The results demonstrate that phase I metabolism in monkeys best approximates that observed in humans, and support the preferred use of this species to investigate possible pharmacokinetic factors that influence the CNS disposition of bupropion and contribute to its high intersubject variability.

RATIONALE In a previous study [Rapid Commun Mass Spectrom. 2004;18:3028-3034], collision-induced dissociation (CID) of [UVI O2 (ClO4 )]+ appeared to be influenced by the high levels of background H2 O in a quadrupole ion trap. The CID of the same species was re-examined here with the goal of determining whether additional, previously obscured dissociation pathways would be revealed under conditions in which the level of background H2 O was lower. METHODS Water- and methanol-coordinated [UVI O2 (ClO4 )]+ precursor ions were generated by electrospray ionization. Multiple-stage tandem mass spectrometry (MSn ) for CID and ion-molecule reaction (IMR) studies was performed using a linear ion trap mass spectrometer. RESULTS Under conditions of low background H2 O, CID of [UVI O2 (ClO4 )]+ generates [UVI O2 (Cl)]+ , presumably by elimination of two O2 molecules. Using low isolation/reaction times, we found that [UVI O2 (Cl)]+ will undergo an IMR with H2 O to generate [UVI O2 (OH)]+ . CONCLUSIONS With lower levels of background H2 O, CID experiments reveal that the intrinsic dissociation pathway for [UVI O2 (ClO4 )]+ leads to [UVI O2 (Cl)]+ , apparently by loss of two O2 molecules. We propose that the results reported in the earlier CID study reflected a two-step process: initial formation of [UVI O2 (Cl)]+ by CID, followed by a very rapid hydrolysis reaction to leave [UVI O2 (OH)]+ .

While the strong axial U O bonds confer high stability and inertness to UO22+, it has been shown that the axial oxo ligands can be eliminated or replaced in the gas-phase using collision-induced dissociation (CID) reactions. In this study, CID of the pentafluorobenzoate precursor ion [UO2(O2C–C6F5)]+ was used to produce the organo-uranyl ion [UO2(C6F5)]+ by decarboxylation. Subsequent CID of [UO2(C6F5)]+ created [UO2(F)]+ by fluoride transfer and elimination of C6F4, rather than UO2+ by elimination of pentafluorophenyl radical (as has been observed for similar species). Moreover, upon reaction of [UO2(C6F5)]+ with H2O, apparent substitution of OH for F to create [UO3HC6F4]+ is favored over hydrolysis to produce [UO2(OH)]+ and (neutral) C6F5H. Subsequent CID of [UO3HC6F4]+ generates [UO2(F)]+ and [OUF]+. When [OUF]+ is isolated to react with H2O and O2 in the ion trap, the principal product ions observed are [UO2(F)]+ and [UO2(OH)]+. Experiments conducted with labeled reagent suggest that reaction with H218O leads to exchange of the oxo ligand and incorporation of the 18O label into [OUF]+ while reaction with O2 likely creates [UO2(F)]+. Formation of [UO2(OH)]+ from [OUF]+ is the result of a cascade of reactions, with initial formation of [UO2(F)]+ by reaction with O2, followed by hydrolysis to create the hydroxide species.

The following gas-phase uranyl/12-crown-4 (12C4) complexes were synthesized by electrospray ionization: [UO2(12C4)2]2+ and [UO2(12C4)2(OH)]+. Collision-induced dissociation (CID) of the dication resulted in [UO2(12C4-H)]+ (12C4-H is a 12C4 that has lost one H), which spontaneously adds water to yield [UO2(12C4-H)(H2O)]+. The latter has the same composition as complex [UO2(12C4)(OH)]+ produced by CID of [UO2(12C4)2(OH)]+ but exhibits different reactivity with water. The postulated structures as isomeric [UO2(12C4-H)(H2O)]+ and [UO2(12C4)(OH)]+ were confirmed by comparison of infrared multiphoton dissociation (IRMPD) spectra with computed spectra. The structure of [UO2(12C4-H)]+ corresponds to cleavage of a C–O bond in the 12C4 ring, with formation of a discrete U–Oeq bond and equatorial coordination by three intact ether moieties. Comparison of IRMPD and computed IR spectra furthermore enabled assignment of the structures of the other complexes. Theoretical studies of the chemical bonding features of the complexes provide an understanding of their stabilities and reactivities. The results reveal bonding and structures of the uranyl/12C4 complexes and demonstrate the synthesis and identification of two different isomers of gas-phase uranyl coordination complexes.

Developing a comprehensive understanding of the reactivity of uranium species remains an important goal in areas ranging from the development of nuclear fuel processing methods to studies of the migration and fate of the element in the environment. Electrospray ionization (ESI) can provide relatively easy access to gas-phase complexes containing uranium in high oxidation states for subsequent studies of intrinsic structure and reactivity. We report here the formation of a superoxo- complex, [UVIO2(O2)(O2C-CF3)2]−, which is created by ESI using “gentle” conditions (low sheath gas flow rate and low desolvation temperature). CID of [UVIO2(O2)(O2C-CF3)2]− causes elimination of O2, presumably with concomitant reduction of UVIO22+ to UVO2+. Remarkably, subsequent CID of [UVO2(O2C-CF3)2]− creates a species at m/z 330, which is attributed to formation of [UVO(F)4]−. A similar species is generated by multiple-stage CID in a linear ion trap, and collision-cell CID in a Fourier-transform ion-cyclotron resonance (FT-ICR) mass spectrometer, when initiated with the tris-trifluoroacetato complex [UVIO2(O2C-CF3)3]−. High accuracy mass measurement using the FT-ICR instrument confirms the composition assignment for the species at m/z 330.

In a previous study [Int. J. Mass Spectrom. 2010; 297: 67–75], the asymmetric O=U=O stretch (ν3) was measured for anionic uranyl complexes with composition [UO2(X)3]-, X = Cl-, Br- and I-. Within this group of complexes, the ν3 frequency red-shifts following the trend I > Br > Cl, suggesting concomitant weakening of the U=O bonds. However, a value for [UO2(F)3]- was not measured, which prevented a comprehensive comparison of measured ν3 positions to computed frequencies from density functional theory (DFT) calculations. Because the shift in ν3 is predicted to be most dramatic when X = F, we revisited these species using infrared multiple-photon photodissociation spectroscopy. As in our earlier study, a modest red-shift to the ν3 vibration of ∼ 6 cm-1 was observed for X = I-, Br-, and Cl-, and the position of the frequency follows the trend I- > Br- > Cl-. The value measured for [UO2(F)3]- is ∼43 cm-1 lower than the one measured for [UO2(Cl)3]-. Overall, the trend with respect to ν3 position is reproduced well by computed frequencies from DFT.

The synthesis, reactivity, structures, and bonding in gas-phase binary and complex oxide anion molecules of protactinium and uranium have been studied by experiment and theory. The oxalate ions, AnVO2(C2O4)−, where An = Pa or U, are essentially actinyl ions, AnVO2+, coordinated by an oxalate dianion. Both react with water to yield the pentavalent hydroxides, AnVO(OH)2(C2O4)−. The chemistry of Pa and U becomes divergent for reactions that result in oxidation: whereas PaVI is inaccessible, UVI is very stable. The UVO2(C2O4)− complex exhibits a remarkable spontaneous exothermic replacement of the oxalate ligand by O2 to yield UO4– and two CO2 molecules. The structure of the uranium tetroxide anion is computed to correspond to distorted uranyl, UVIO22+, coordinated in the equatorial plane by two equivalent O atoms each having formal charges of −1.5 and U–O bond orders intermediate between single and double. The unreactive nature of PaVO2(C2O4)− toward O2 is a manifestation of the resistance toward oxidation of PaV, and clearly reveals the disparate chemistries of Pa and U. The uranium tetroxide anion, UO4–, reacts with water to yield UO5H2–. Infrared spectra obtained for UO5H2– confirm the computed lowest-energy structure, UO3(OH)2–.

© The Royal Society of Chemistry 2016. Understanding of the nature and extent of chemical bonding in uranyl coordination complexes is crucial for the design of new ligands for nuclear waste separation, uranium extraction from seawater, and other applications. We report here the synthesis, infrared spectroscopic characterization, and quantum chemical studies of a molecular uranyl-di-15-crown-5 complex. The structure and bonding of this unique complex featuring a distinctive 6-fold coplanar coordination staggered sandwich structure and an unusual non-perpendicular orientation of the uranyl moiety are evaluated using density functional theory and chemical bonding analyses. The results provide fundamental understanding of the coordination interaction of uranyl with oxygen-donor ligands.

RATIONALE The lower levels of adventitious H2 O in a linear ion trap allow the fragmentation reactions of [UO2 OCH3 ](+) and [UO2 OCH2 CH3 ](+) to be examined in detail. METHODS Methanol- and ethanol-coordinated UO2 (2+) -alkoxide precursors were generated by electrospray ionization (ESI). Multiple-stage tandem mass spectrometry (MS(n) ) and collision-induced dissociation (CID) were performed using a linear ion trap mass spectrometer. RESULTS CID of [UO2 OCH3 (CH3 OH)n ](+) and [UO2 OCH2 CH3 (CH3 CH2 OH)n ](+) , n = 3 and 2, causes loss of neutral alcohol ligands, leading ultimately to bare uranyl-alkoxide species. Comparison of 'native' to deuterium-labeled precursors reveals dissociation pathways not previously observed in 3-D ion trap experiments. CONCLUSIONS UO2 H(+) is generated from [UO2 OCH3 ](+) by transfer of H from the methyl group. Variable-energy and variable-time CID experiments suggest that the apparent threshold for production of UO2 H(+) is lower than for UO2 (+) , but the pathway is kinetically less favored for the former than for the latter. CID experiments reveal that [UO2 OCH2 CH3 ](+) dissociates to generate [UO2 CH3 ](+) , a relatively rare species with a U-C bond, and [UO2 (O = CH2 )](+) .

Past studies of fragmentation reactions of doubly-charged uranyl (UO22+) complexes have been impeded by very rapid water addition reactions that cause H2O adducts to dominate product ion spectra. The fragmentation of uranyl-acetone (aco) complexes ([UO2(aco)n]2+, n = 1–5), generated by electrospray ionization, is revisited here using: (a) collisional activation in a linear ion trap (LIT) mass spectrometer in which the level of background H2O is significantly lower, and (b) infrared multiple-photon photodissociation (IRMPD, 10.6 μm) in the LIT and a Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometer. Lower levels of adventitious H2O in the LIT provided access to fragmentation of [UO2(aco)n]2+, n = 1–5. For n = 3–5, direct elimination of aco ligands is the favored fragmentation pathway. For n = 1 and 2, charge reduction reactions are dominant. For [UO2(aco)2]2+, the most abundant product ion is [UO2(aco)]+, while UO2+ is observed following collision-induced dissociation (CID) of [UO2(aco)]2+. Minor peaks corresponding to ligated [UO2OH]+ are also observed. The IRMPD experiments in the FT-ICR yielded highly accurate mass measurements that confirm composition assignments, and shed light on dissociation reactions in a gas-phase environment that is entirely free of adventitious H2O. For [UO2(aco)n]2+, n = 3–5, the primary photodissociation channel is direct aco elimination, along with charge-reduction pathways that involve intra-complex proton transfer and formation of species that contain enolate ligands. Similar pathways are observed for IRMPD measurements in the LIT.

In this study, peptides were derivatized by reaction with salicylaldehyde to create N-terminal imines (Schiff bases). Collision-induced dissociation of the imine-modified peptides produces a complete series of b and a ions (which reveal sequence). However, an unusual pathway is also observed, one that leads to elimination of the residue mass of the N-terminal amino acid despite the chemical modification to create the imine. This pathway was investigated further using infrared multiple-photon dissociation (IRMPD) spectroscopy and density functional theory with alanine-glycine-glycine (AGG) as the test peptide. The IRMPD spectrum for the product generated by loss of 71 from modified AGG (Sal-AGG) matches one predicted for protonated Sal-GG, as well as the IRMPD spectrum of glycine-glycine derivatized independently to produce a Schiff base. We conclude that the residue mass of the N-terminal amino acid is likely eliminated through a pathway that involves nucleophilic attack by an amide N atom and possible formation of an imidazole-4-one intermediate.

© 2017 American Chemical Society. Recent efforts to activate the strong uranium-oxygen bonds in the dioxo uranyl cation have been limited to single oxo-group activation through either uranyl reduction and functionalization in solution, or by collision induced dissociation (CID) in the gas-phase, using mass spectrometry (MS). Here, we report and investigate the surprising double activation of uranyl by an organic ligand, 3,4,3-LI(CAM), leading to the formation of a formal U6+chelate in the gas-phase. The cleavage of both uranyl oxo bonds was experimentally evidenced by CID, using deuterium and18O isotopic substitutions, and by infrared multiple photon dissociation (IRMPD) spectroscopy. Density functional theory (DFT) computations predict that the overall reaction requires only 132 kJ/mol, with the first oxygen activation entailing about 107 kJ/mol. Combined with analysis of similar, but unreactive ligands, these results shed light on the chelation-driven mechanism of uranyl oxo bond cleavage, demonstrating its dependence on the presence of ligand hydroxyl protons available for direct interactions with the uranyl oxygens.

Neutral complexes of zinc with N,N′-diisopropylpiperazine-2,3-dithione (iPr2Dt0) and N,N′-dimethylpiperazine-2,3-dithione (Me2Dt0) with chloride or maleonitriledithiolate (mnt2−) as coligands have been synthesized and characterized. The molecular structures of these zinc complexes have been determined using single crystal X-ray diffractometry. Complexes recrystallize in monoclinic P type systems with zinc adopting a distorted tetrahedral geometry. Two zinc complexes with mixed-valence dithiolene ligands exhibit ligand-to-ligand charge transfer bands. Optimized geometries, molecular vibrations and electronic structures of charge-transfer complexes were calculated using density functional theory (B3LYP/6-311G+(d,p) level). Redox orbitals are shown to be almost exclusively ligand in nature, with a HOMO based heavily on the electron-rich maleonitriledithiolate ligand, and a LUMO comprised mostly of the electron-deficient dithione ligand. Charge transfer is thus believed to proceed from dithiolate HOMO to dithione LUMO, showing ligand-to-ligand redox interplay across a d10 metal.

Combined collision-induced dissociation mass spectrometry experiments with DFT and MP2 calculations were employed to elucidate the molecular structures and energetics of dissociation reactions of uranyl species containing acetone and diacetone alcohol ligands. It is shown that solutions containing diacetone alcohol ligands can produce species with more than five oxygen atoms available for coordination. Calculations confirm that complexes with up to four diacetone alcohol ligands can be energetically stable but that the effective number of atoms coordinating with uranium in the equatorial plane does not exceed five. Water elimination reactions of diacetone alcohol ligands are shown to have two coordination-dependent reaction channels, through formation of mesityl oxide ligands or formation of alkoxide and protonated mesityl oxide species. The present results provide an explanation for the implausible observation of "[UO(2)(ACO)(6,7,8)](2+)" in and observed water-elimination reactions from purportedly uranyl-acetone complexes (Rios, D.; Rutkowski, P. X.; Van Stipdonk, M. J.; Gibson, J. K. Inorg. Chem. 2011, 50, 4781).

Collision-induced dissociation (CID) of the peptide alanine-4-aminomethylbenzoic acid-glycine, A(AMBz)G generates a prominent b(2) ion despite a previous report [ER. Talaty, T.J. Cooper, S.M. Osburn, M.J. Van Stipdonk, Collision-induced dissociation of protonated tetrapeptides containing beta-alanine, gamma-aminobutyric acid, e-aminocaproic acid or 4-aminomethylbenzoic acid residues, Rapid Commun. Mass Spectrom. 20 (2006) 3443-3455] which showed that incorporation of the aromatic amino acid into a peptide sequence inhibits generation of b(n) ions formed by cleavage to the immediate C-terminal side of the residue. Infrared multiple photon dissociation (IRMPD) spectroscopy and density functional theory (DFT) calculations suggest that the b(2) ion generated from A(AMBz)G has an acylium structure. The b2 ion generated from (AMBz)AG, in which the aromatic residue is situated at the amino-terminus, is instead a conventional oxazolone. (c) 2012 Elsevier B.V. All rights reserved.

Nickel Superoxide Dismutase (NiSOD) and the A-cluster of Carbon Monoxide Dehydrogenase/Acetyl Coenzyme A Synthase (CODH/ACS) both feature active sites with Ni coordinated by thiolate and amide donors. It is likely that the particular set of donors is important in tuning the redox potential of the Ni center(s). We report herein an expansion of our efforts involving the use of 2,2′-dithiodibenzaldehyde (DTDB) as a synthon for metal–thiolate complexes to reactions with Ni complexes of N,N-dimethylethylenediamine (dmen). In the presence of coordinating counterions, these reactions result in monomeric square-planar complexes of the tridentate N2S donor ligand derived from the Schiff-base condensation of dmen and DTDB. In the absence of a coordinating counterion, we have isolated a Ni(II) complex with an asymmetric N2S2 donor set involving one amine and one imine N donor in addition to two thiolate donors. This latter complex is discussed with respect to its relevance to the active site of NiSOD.

We present infrared photodissociation spectra of two protonated peptides that are cooled in a ~10 K quadrupole ion trap and "tagged" with weakly bound H(2) molecules. Spectra are recorded over the range of 600-4300 cm(-1) using a table-top laser source, and are shown to result from one-photon absorption events. This arrangement is demonstrated to recover sharp (Δν ~6 cm(-1)) transitions throughout the fingerprint region, despite the very high density of vibrational states in this energy range. The fundamentals associated with all of the signature N-H and C=O stretching bands are completely resolved. To address the site-specificity of the C=O stretches near 1800 cm(-1), we incorporated one (13)C into the tripeptide. The labeling affects only one line in the complex spectrum, indicating that each C=O oscillator contributes a single distinct band, effectively "reporting" its local chemical environment. For both peptides, analysis of the resulting band patterns indicates that only one isomeric form is generated upon cooling the ions initially at room temperature into the H(2) tagging regime.

The infrared spectrum of the bis-uranyl nitrate complex [(UO(2))(2)(NO(3))(5)](-) was measured in the gas phase using multiple photon dissociation (IRMPD). Intense absorptions corresponding to the nitrate symmetric and asymmetric vibrations, and the uranyl asymmetric vibration were observed. The nitrate nu(3) vibrations indicate the presence of nitrate in a bridging configuration bound to both uranyl cations, and probably two distinct pendant nitrates in the complex. The coordination environment of the nitrate ligands and the uranyl cations were compared to those in the mono-uranyl complex. Overall, the uranyl cation is more loosely coordinated in the bis-uranyl complex [(UO(2))(2)(NO(3))(5)](-) compared to the mono-complex [UO(2)(NO(3))(3)](-), as indicated by a higher O-U-O asymmetric stretching (nu(3)) frequency. However, the pendant nitrate ligands are more strongly bound in the bis-complex than they are in the mono-uranyl complex, as indicated by the nu(3) frequencies of the pendant nitrate, which are split into nitrosyl and O-N-O vibrations as a result of bidentate coordination. These phenomena are consistent with lower electron density donation per uranyl by the nitrate bridging two uranyl centers compared to that of a pendant nitrate in the mono-uranyl complex. The lowest energy structure predicted by density functional theory (B3LYP functional) calculations was one in which the two uranyl molecules bridged by a single nitrate coordinated in a bis-bidentate fashion. Each uranyl molecule was coordinated by two pendant nitrate ligands. The corresponding vibrational spectrum was in excellent agreement with the IRMPD measurement, confirming the structural assignment. (C) 2011 Elsevier B.V. All rights reserved.

The intrinsic binding of halide ions to the metal center in the uranyl molecule is a topic of ongoing research interest in both the actinide separations and theoretical communities. Investigations of structure in the condensed phases is frequently obfuscated by solvent interactions, that can alter ligand binding and spectroscopic properties. The approach taken in this study is to move the uranyl halide complexes into the gas phase where they are free from solvent interactions, and then interrogate their vibrational spectroscopy using infrared multiple photon dissociation (IRMPD). The spectra of cationic coordination complexes having the composition [UO2(X)(ACO)3]+ (X = F, Cl, Br and I; ACO = acetone) were acquired using electrospray for ion formation, and monitoring the ion signal from the photoelimination of ACO ligands. The studies showed that the asymmetric v3 UO2 frequency was insensitive to halide identity as X was varied from Cl to I, suggesting that in these pseudo octahedral complexes, changing the nucleophilicity of the halide did not appreciably alter the binding in the complex. The v3 peak in the spectrum of the F-containing complex was ~ 10 cm-1 lower indicating stronger coordination in this complex. Similarly the ACO carbonyl stretches showed that the C=O frequency wasmore » relatively insensitive to the identity of the halide, although a modest shift to the blue was seen for the complexes with the more nucleophilic anions, consistent with the idea that they loosen solvent binding. Surprisingly, the v1 stretch was activated when the softer anions Cl, Br and I were present in the complexes. IR studies of the anionic complexes were conducted by measuring the v3 UO2 frequencies of [UO2X3]-, where X = Cl-, Br- and I-. The trifluoro complex could not be photodissociated. In these negatively charged complexes, the UO2 v3 values decreased with increasing anion nucleophilicity. This observation was consistent with DFT calculations that indicated that dissociation energy decreased on the order F > Cl > Br > I.« less

Multiple-stage tandem mass spectrometry and collision-induced dissociation were used to investigate loss of H(2)O or CH(3)OH from protonated versions of GGGX (where X = G, A, and V), GGGGG, and the methyl esters of these peptides. In addition, wavelength-selective infrared multiple photon dissociation was used to characterize the [M + H - H(2)O](+) product derived from protonated GGGG and the major MS(3) fragment, [M + H - H(2)O - 29](+) of this peak. Consistent with the earlier work [ Ballard , K. D. ; Gaskell , S. J. J. Am. Soc. Mass Spectrom. 1993 , 4 , 477 - 481 ; Reid , G. E. ; Simpson , R. J. ; O'Hair , R. A. J. Int. J. Mass Spectrom. 1999 , 190/191 , 209 -230 ], CID experiments show that [M + H - H(2)O](+) is the dominant peak generated from both protonated GGGG and protonated GGGG-OMe. This strongly suggests that the loss of the H(2)O molecule occurs from a position other than the C-terminal free acid and that the product does not correspond to formation of the b(4) ion. Subsequent CID of [M + H - H(2)O](+) supports this proposal by resulting in a major product that is 29 mass units less than the precursor ion. This is consistent with loss of HN horizontal lineCH(2) rather than loss of carbon monoxide (28 mass units), which is characteristic of oxazolone-type b(n) ions. Comparison between experimental and theoretical infrared spectra for a group of possible structures confirms that the [M + H - H(2)O](+) peak is not a substituted oxazolone but instead suggests formation of an ion that features a five-membered ring along the peptide backbone, close to the amino terminus. Additionally, transition structure calculations and comparison of theoretical and experimental spectra of the [M + H - H(2)O - 29](+) peak also support this proposal.

Tris-carboxylate complexes of uranyl [UO2](2+) with acetate and benzoate were generated using electrospray ionization mass spectrometry, and then isolated in a Fourier transform ion cyclotron resonance mass spectrometer. Wavelength-selective infrared multiple photon dissociation (IRMPD) of the tris-acetato uranyl anion resulted in a redox elimination of an acetate radical, which was used to generate an IR spectrum that consisted of six prominent absorption bands. These were interpreted with the aid of density functional theory calculations in terms of symmetric and antisymmetric -CO2 stretches of the monodentate and bidentate acetate, CH3 bending and umbrella vibrations, and a uranyl O-U-O asymmetric stretch. The comparison of the calculated and measured IR spectra indicated that the predominant conformer of the tris-acetate complex contained two acetate ligands bound in a bidentate fashion, while the third acetate was monodentate. In similar fashion, the tris-benzoate uranyl anion was formed and photodissociated by loss of a benzoate radical, enabling measurement of the infrared spectrum that was in close agreement with that calculated for a structure containing one monodentate and two bidentate benzoate ligands. (J Am Soc Mass Spectrom 2010, 21, 719-727) (C) 2010. Published by Elsevier Inc. on behalf of American Society for Mass Spectrometry

Infrared multiple photon dissociation (IRMPD) spectroscopy was used to study formation of b2+ from nicotinyl-glycine-glycine-methyl ester (NicGGOMe). IRMPD shows that NicGGOMe is protonated at the pyridine ring of the nicotinyl group, and more importantly, that b2+ from NicGGOMe is not protonated at the oxazolone ring, as would be expected if the species were generated on the conventional bn+/yn+ oxazolone pathway, but at the pyridine ring instead. IRMPD data support a hypothesis that formation of b2+ from NicGGOMe involves mobilization and transfer of an amide position proton during the fragmentation reaction.

Cerium oxyhydroxide cluster anions were produced by irradiating ceric oxide particles by using 355 nm laser pulses that were synchronized with pulses of nitrogen gas admitted to the irradiation chamber. The gas pulse stabilized the nascent clusters that are largely anhydrous [Ce(x)O(y)] ions and neutrals. These initially formed species react with water, principally forming oxohydroxy species that are described by the general formula [Ce(x)O(y)(OH)(z)](-) for which all the Ce atoms are in the IV oxidation state. In general, the extent of hydroxylation varies from a value of three OH per Ce atom when x = 1 to a value slightly greater than 1 for x >or= 8. The Ce(3) and Ce(6) species deviate significantly from this trend: the x = 3 cluster accommodates more hydroxyl moieties compared to neighboring congeners at x = 2 and 4. Conversely, the x = 6 cluster is significantly less hydroxylated than its x = 5 and 7 neighbors. Density functional theory (DFT) modeling of the cluster structures shows that the hydrated clusters are hydrolyzed, and contain one-to-multiple hydroxide moieties, but not datively bound water. DFT also predicts an energetic preference for formation of highly symmetric structures as the size of the clusters increases. The calculated structures indicate that the ability of the Ce(3) oxyhydroxide to accommodate more extensive hydroxylation is due to a more open, hexagonal structure in which the Ce atoms can participate in multiple hydrolysis reactions. Conversely the Ce(6) oxyhydroxide has an octahedral structure that is not conducive to hydrolysis. In addition to the fully oxidized (Ce(IV)) oxyhydroxides, reduced oxyhydroxides (containing a Ce(III) center) are also formed. These become more prominent as the size of the clusters increases, suggesting that the larger ceria clusters have an increased ability to accommodate a reduced Ce(III) moiety. In addition, the spectra offer evidence for the formation of superoxide derivatives that may arise from reaction of the reduced oxyhydroxides with dioxygen. The overall intensity of the clusters tends to monotonically decrease as the cluster size increases; however, this trend is interrupted at Ce(13), which is significantly more stable compared to neighboring congeners, suggesting formation of a dehydrated Keggin-type structure.

The syntheses, characterization, and single-crystal X-ray crystal structures are reported for four complexes of iron and cobalt with the pentadentate ligands, 2,6-diacetylpyridinebis(thiosemicarbazone) (H2L1) and 2,6-diacetylpyridinebis(phenylthiosemicarbazone) (H2L2), including a cobalt dimer displaying a deviation from planarity which is unprecedented for this class of ligands and allows the ligand to occupy five positions of a pseudo-octahedral coordination sphere. This dimer reacts with KCN to produce a mononuclear complex of relevance to the active site of cobalt nitrile hydratase.

Gas-phase complexes of the formula [UO_2(lig)]^+ (lig = acetone (aco) or dimethylsulfoxide (dmso)) were generated by electrospray ionization (ESI) and studied by tandem ion-trap mass spectrometry to determine the general effect of ligand charge donation on the reactivity of UO_2^+ with respect to water and dioxygen. The original hypothesis that addition of O_2 is enhanced by strong σ-donor ligands bound to UO_2^+ is supported by results from competitive collision-induced dissociation (CID) experiments, which show near exclusive loss of H_2O from [UO_2(dmso)(H_2O)(O_2)]^+, whereas both H_2O and O_2 are eliminated from the corresponding [UO_2(aco)(H_2O)(O_2)]^+ species. Ligand-addition reaction rates were investigated by monitoring precursor and product ion intensities as a function of ion storage time in the ion-trap mass spectrometer: these experiments suggest that the association of dioxygen to the UO_2^+ complex is enhanced when the more basic dmso ligand was coordinated to the metal complex. Conversely, addition of H_2O is favored for the analogous complex ion that contains an aco ligand. Experimental rate measurements are supported by density function theory calculations of relative energies, which show stronger bonds between UO_2^+ and O_2 when dmso is the coordinating ligand, whereas bonds to H_2O are stronger for the aco complex.

Extensive (15)N labeling and multiple-stage tandem mass spectrometry were used to investigate the fragmentation pathways of the model peptide FGGFL during low-energy collision-induced-dissociation (CID) in an ion-trap mass spectrometer. Of particular interest was formation of a(4) from b(4) and a(4) (a(4)-NH(3)) from a(4) ions correspondingly, and apparent rearrangement and scrambling of peptide sequence during CID. It is suggested that the original FGGF(oxa)b(4) structure undergoes b-type scrambling to form GGFF(oxa). These two isomers fragment further by elimination of CO and (14)NH(3) or (15)NH(3) to form the corresponding a(4)and a(4) isomers, respectively. For ((15)N-F)GGFL and FGG((15)N-F)L the a(4) ion population appears as two distinct peaks separated by 1 mass unit. These two peaks could be separated and fragmented individually in subsequent CID stages to provide a useful tool for exploration of potential mechanisms along the a(4) --> a(4) pathway reported previously in the literature (Vachet et al. J. Am. Chem. Soc.1997, 119, 5481, and Cooper et al. J. Am. Soc. Mass Spectrom.2006, 17, 1654). These mechanisms result in formally the same a(4) structures but differ in the position of the expelled nitrogen atom. Detailed analysis of the observed fragmentation patterns for the separated light and heavy a(4) ion fractions of ((15)N-F)GGFL indicates that the mechanism proposed by Cooper et al. is consistent with the experimental findings, while the mechanism proposed by Vachet et al. cannot account for the labeling data. In addition, a new rearrangement pathway is presented for a(4)-CO ions that effectively transfers the former C-terminal amino acid residue to the N-terminus.

Electrospray ionization was used to generate doubly charged complex ions composed of the uranyl ion and nitrile ligands. The complexes, with general formula [UO2(RCN)n]2+, n = 0-5 (where R=CH3-, CH3CH2-, or C6H5-), were isolated in an ion-trap mass spectrometer to probe intrinsic reactions with H2O. For these complexes, two general reaction pathways were observed: (a) the direct addition of one or more H2O ligands to the doubly charged complexes and (b) charge-reduction reactions. For the latter, the reactions produced uranyl hydroxide, [UO2OH], complexes via collisions with gas-phase H2O molecules and the elimination of protonated nitrile ligands.

We report a new fragmentation pathway for the CID of (b3 - 1 + Cat)+ product ions derived from the model peptide AXAG, where X = beta-alanine, gamma-aminobutyric acid, epsilon-amino-n-caproic acid, or 4-aminomethylbenzoic acid. By changing the amino acid to the C-terminal side of the amino acid X, and incorporating 15N and 13C labeled residues at the same position, we conclude that the dissociation pathway most likely leads to a metal cationized nitrile. With respect to the various amino acids at position X, the putative nitrile product becomes more prominent, relative to the conventional (a3 - 1 + Cat)+ species, in the order beta-alanine < gamma-aminobutyric acid < epsilon-aminocaproic acid < 4-aminomethylbenzoic acid. The pathway is not observed for peptides with alpha-amino acids at position X. The product ion is observed most prominently during the CID of Li+ and Na+ cationized peptides, only to a small extent for Ag+ cationized peptides, and not at all from protonated analogues.

We report here that electrospray ionization (ESI) of uranyl nitrate dissolved in a mixture of H 2 O and acetone causes the formation of doubly charged, gas-phase complexes containing UO 2 2 + "solvated" by neutral ligands.Using mild conditions, the dominant species observed in the ESI mass spectrum contained the uranyl ion coordinated by five acetone ligands, consistent with proposed most-stable structures in the solution phase. However, chemical mass shift data, ion peak shapes, and a plot of fractional ion abundance versus ion desolvation temperature suggest that in the gas phase, and under the ion-trapping and ejection conditions imposed, complexes with five equatorial acetone ligands are less stable than those with four. Multiple-stage tandem mass spectrometry showed that uranyl-acetone complexes dissociate via the elimination of acetone ligands and through pathways that involve reactive collisions with adventitious H 2 O in the ion trap. At no point was complete removal of ligands to generate the UO 2 2 + ion achieved. ESI was also used to generate complex ions of similar composition and ligand number but different charge state for an investigation of the influence of complex charge on the tendency to add ligands by gas-phase association reactions. We found that the addition of a fifth acetone molecule to complexes initially containing four equatorial ligands is more facile for the doubly charged species. The singly charged complex shows a significant back-reaction to eliminate the fifth ligand, suggesting an intrinsic difference in the preferred coordination number for the U(VI) and U(V) complexes in the gas phase.

We demonstrate, by way of multi-stage tandem mass spectrometry and extensive deuterium labeling, that 2-propanol is converted to acetone, and 2-propoxide to acetaldehyde, when monopositive 2-propanol-coordinated uranyl-ligand cations are subjected to collision-induced dissociation in the gas-phase environment of an ion trap mass spectrometer. A species with formula [(UO2OCH(CH3)2)(HOCH(CH3)2)]+, derived from dissociation of the gas-phase precursor [(UO2NO3)(HOCH(CH3)2)3]+ eliminates two H atoms and CH3 in consecutive stages to generate a monopositive complex composed of the U(V) species U O 2 + coordinated by acetone and acetaldehyde, i.e. [ U O 2 + (O C(CH3)2)(O C(H)CH3)]. Dissociation of this latter ion resulted in elimination of the two coordinating carbonyl ligands in two consecutive dissociation stages to leave U O 2 + . Analogous reactions were not observed for uranyl complexes containing 1-propanol or 2-methyl-2-propanol, or for cationic complexes with divalent metals such as Ni2+, Co2+, Pb2+ and Ca2+. One explanation for these reactions is bond insertion by the metal center in the bis-ligated uranyl complex, which would be expected to have an LUMO consisting of unoccupied 6d-orbitals that would confer transition metal-like behavior on the complex.

The reactivity of mono-alcohol/Ag+ complexes (methanol, ethanol, n-propanol, n-butanol, and tert-butyl alcohol) when stored, without collisional activation, in an ion trap mass spectrometer for periods ranging from 1 to 1000 ms was investigated. During the isolation/reaction time, association reactions between the complex ions and adventitious water and alcohol present within a He bath gas occurred to varying degrees. While the free Ag+ ion was unreactive, complexes composed of Ag+ coordinated by a single alcohol molecule demonstrated reactivity consistent with the following reactions: (1) formation of an adduct by the addition of a single water molecule, (2) formation of a bis-alcohol complex by the addition of a second alcohol molecule, and (3) formation of the bis-alcohol complex via the exchange of a water molecule for alcohol when investigated under similar experimental conditions. The trend in reactivity followed the order n-butanol > n-propanol > ethanol > methanol. To quantify observed trends in ...

The syntheses of cationic nickel complexes using N,N'-dimethyl piperazine 2,3-dithione (Me2Dt(0)) and N,N'-diisopropyl piperazine 2,3-dithione ((i)Pr2Dt(0)) ligands are reported. These ligands were used in synthesizing bis and tris(dithione)Ni(II) complexes as tetrafluoroborate or hexafluorophosphate salts, i.e., [Ni((i)Pr2Dt(0))2][BF4]2 ([1a][BF4]2), [Ni((i)Pr2Dt(0))2][PF6]2 ([1a][PF6]2), [Ni(Me2Dt(0))2][BF4]2 ([1b][BF4]2), [Ni((i)Pr2Dt(0))3][BF4]2 ([2a][BF4]2), and [Ni((i)Pr2Dt(0))3][PF6]2 ([2a][PF6]2), respectively. Complex [2a][PF6]2 was isolated from a methanolic solution of [1a][PF6]2. Compound [1a][BF4]2 crystallizes in a trigonal crystal system (space group, P31/c) and exhibits unique packing features, whereas [2a][BF4]2 crystallizes in a monoclinic (P21/n) space group. Cyclic voltammograms of [1a][BF4]2 and [1b][BF4]2 are indicative of four reduction processes associated with stepwise single-electron reduction of the ligands. Spectroelectrochemical experiments on [1a][BF4]2 exhibit an intervalence charge transfer (IVCT) transition as a spectroscopic signature of the mixed-valence [Ni((i)Pr2Dt(0))((i)Pr2Dt(1-))](-) species. Analysis of this IVCT band suggests that this ligand based mixed valence complex, [Ni((i)Pr2Dt(0))((i)Pr2Dt(1-))](-), behaves more like a traditional class II/III metal based mixed-valence complex. The density functional theory (DFT) and time dependent DFT calculations provide a theoretical framework for understanding the electronic structures and the nature of excited states of the target compounds that are consistent with their spectroscopic and redox properties. Vibrational spectra of [1a](2+) and [2a](2+) were investigated as discrete species in the gas phase using infrared multiple photon dissociation (IRMPD) spectroscopy.

The gas-phase complex UO2(TMOGA)(2)(2+) (TMOGA = tetramethyl-3-oxa-glutaramide) prepared by electrospray ionization was characterized by infrared multiphoton dissociation (IRMPD) spectroscopy. The IRMPD spectrum from 700-1800 cm(-1) was interpreted using a computational study based on density functional theory. The predicted vibrational frequencies are in good agreement with the measured values, with an average deviation of only 8 cm(-1) (

In a prior study [Van Stipdonk; et al. J. Phys. Chem. A 2006, 110, 959-970], electrospray ionization (ESI) was used to generate doubly charged complex ions composed of the uranyl ion and acetonitrile (acn) ligands. The complexes, general formula [UO2(acn)n](2+), n = 0-5, were isolated in an 3-D quadrupole ion-trap mass spectrometer to probe intrinsic reactions with H2O. Two general reaction pathways were observed: (a) the direct addition of one or more H2O ligands to the doubly charged complexes and (b) charge-exchange reactions. For the former, the intrinsic tendency to add H2O was dependent on the number and type of nitrile ligand. For the latter, charge exchange involved primarily the formation of uranyl hydroxide, [UO2OH](+), presumably via a collision with gas-phase H2O and the elimination of a protonated nitrile ligand. Examination of general ion fragmentation patterns by collision-induced dissociation, however, was hindered by the pronounced tendency to generate hydrated species. In an update to this story, we have revisited the fragmentation of uranyl-acetonitrile complexes in a linear ion-trap (LIT) mass spectrometer. Lower partial pressures of adventitious H2O in the LIT (compared to the 3-D ion trap used in our previous study) minimized adduct formation and allowed access to lower uranyl coordination numbers than previously possible. We have now been able to investigate the fragmentation behavior of these complex ions completely, with a focus on tendency to undergo ligand elimination versus charge reduction reactions. CID can be used to drive ligand elimination to completion to furnish the bare uranyl dication, UO2(2+). In addition, fragmentation of [UO2(acn)](2+) generated [UO2(NC)](+), which subsequently fragmented to furnish NUO(+). Formation of the nitrido by transfer of N from cyanide was confirmed using precursors labeled with (15)N. The observed formation of [UO2(NC)](+) and NUO(+) was modeled by density functional theory.

Aminoethanethiol (AET), at an appropriate pH, forms a charged self-assembled monolayer (SAM) on Au surfaces. We have shown that an AET-SAM can be used to adsorb organic and inorganic anions from aqueous and ethanol solutions. The adsorbed anions can then be sputtered with high efficiency for characterization by time-of-flight secondary ion mass spectrometry. We present here the application of the AET monolayer for the characterization of more complex and biologically relevant organic sulfates and phosphates up to 1150 Daltons, each featuring a charged anionic site to facilitate the adsorption to the monolayer by ion-pair formation. We monitored the mass spectra and secondary ion emission following 20 keV (CsI)nCs+ (n=0–2) projectile impacts on targets composed of thin layers deposited on Si, Au, and AET/Au substrates; and of thick targets (thick with respect to the 10–100 nm range of projectile). For each molecule used in this study, the secondary ion yield increased when the anion was deposited as a thin layer, relative to a thick layer, and is greatest for AET/Au substrates compared to bare Au and polished Si substrates. Additionally, the intact-to-fragment ion yield ratio is lower when sputtering from the solid salt target than from the AET monolayer.

During our ongoing investigation of the formation and reactivity of gas-phase complex ions composed of Ag(I) and various α-amino acids, we discovered that the mass-to-charge ratio for the major collision-induced dissociation (CID) product generated from a binary Ag+ complex with phenylalanine was consistent with the formation of an Ag+ complex with an aldehyde. In this study we investigated and compared the fragmentation pathways for complexes of Ag+ with phenylalanine, phenylalanine with exchangeable protium replaced with deuterium, phenylalanine with the carboxylic acid group labeled with 13C, and phenylalanine with the benzylic group labeled with deuterium. The reaction pathways were determined using multidimensional dissociation steps in an ion-trap mass spectrometer. The dissociation experiments provide clear evidence for the formation of several novel product species, including the Ag+ complex with phenylacetaldehyde, as well as the formation of an Ag+ complex with either a benzyl carbene or styrene...

With the increased application of polyatomic primary ions for organic secondary ion mass spectrometry, a method to compare the performance of the various available projectiles is needed. In this work, primary ion performance was evaluated based on analyte-specific secondary ion yield, the amount of fragmentation, and the amount of metastable decay induced by each primary ion. These measurements were used to construct a projectile efficiency number for each primary ion applied to a specific analyte. An organic acid, phospholipids, and alkyl sulfates, prepared as multilayer and monolayer surfaces were analyzed with various atomic and polyatomic primary ions. It was found that polyatomic primary ions are best suited for multilayer organic samples whereas atomic primary ions are most effective for monolayer organic samples. Results are compared to other studies that measure the ion formation efficiency of various primary ions.

Secondary ion mass spectrometry was used to monitor the exchange of tetrafluoro- and tetraphenylborate anions to the surface of an amine-terminated self-assembled monolayer. The exchanged surfaces were prepared by soaking aminoethanethiol (AET) monolayers on Au in solutions of the respective sodium salts. The mass spectra produced from the monolayer surface and those from Au blank and propanethiol monolayers soaked in the same salt solutions demonstrate that the protonated amine terminus of the AET monolayer is important to the uptake of the inorganic anion. The exchanged monolayer surfaces were used to measure secondary ion yields produced from ultrathin films by (CsI)nCs+ (n = 0−2) projectiles at the limit of single-ion impacts. The yield trends produced from the monolayer surface as a function of projectile complexity and energy differ dramatically from those generated from thicker targets of solid NaBF4 and NaB(Ph)4. Nonlinear enhancements (expressed as an increase in the secondary ion yield per proje...

Electrospray ionization (ESI) in the negative ion mode was used to create anionic, gas-phase oxo-molybdenum complexes with dithiolene ligands. By varying ESI and ion transfer conditions, both doubly and singly charged forms of the complex, with identical formulas, could be observed. Collision-induced dissociation (CID) of the dianion generated exclusively the monoanion, while fragmentation of the monoanion involved decomposition of the dithiolene ligands. The intrinsic structure of the monoanion and the dianion were determined by using wavelength-selective infrared multiple-photon dissociation (IRMPD) spectroscopy and density functional theory calculations. The IRMPD spectrum for the dianion exhibits absorptions that can be assigned to (ligand) C=C, C-S, C-C N, and Mo=O stretches. Comparison of the IRMPD spectrum to spectra predicted for various possible conformations allows assignment of a pseudo square pyramidal structure with C-2 nu, symmetry, equatorial coordination of MoO2+ by the S atoms of the dithiolene ligands, and a singlet spin state. A single absorption was observed for the oxidized complex. When the same scaling factor employed for the dianion is used oxidized version, theoretical spectra suggest that the absorption is the Mo=O stretch for a distorted square pyramidal structure and doublet spin state. A predicted change in conformation upon oxidation of the dianion is consistent with a proposed bonding scheme for the bent-metallocene dithiolene compounds [Lauher, J. W.; Hoffmann, R. J. Am. Chem. Soc. 1976, 98, 1729-1742], where a large folding of the dithiolene moiety along the S center dot center dot center dot S vector is dependent on the occupancy of the in-plane metal d-orbital.

Collision-induced dissociation (CID) of protonated 2-hydroxynicotinic acid (2-OHNic) generates a dominant product ion through loss of 18 mass units, presumably the elimination of water. Subsequent isolation and storage of this product ion in the gas-phase environment of an ion trap mass spectrometer, without imposed collisional activation, shows that the species undergoes addition reactions to furnish new products that are higher in mass by 18 and 32 units. Density functional theory (DFT) calculations suggest that an acylium ion (i.e., loss of H2O from the acid group) is energetically more favored than is a species generated by elimination of H2O from the hydroxypyridine ring. Formation of the acylium product is confirmed by comparing the infrared multiple photon dissociation (IRMPD) spectrum to theoretical spectra from (DFT) harmonic calculations for several possible isomers. A thorough DFT study of the reaction dynamics suggests that the acylium ion is generated from the global minimum for the protonated precursor along a pathway that involves proton transfer from the hydroxypyridine ring and elimination of OH from the acid group.

Electrospray ionization of actinyl perchlorate solutions in H(2)O with 5% by volume of dimethylformamide (DMF) produced the isolatable gas-phase complexes, [An(VI)O(2)(DMF)(3)(H(2)O)](2+) and [An(VI)O(2)(DMF)(4)](2+), where An = U, Np, and Pu. Collision-induced dissociation confirmed the composition of the dipositive coordination complexes, and produced doubly- and singly-charged fragment ions. The fragmentation products reveal differences in underlying chemistries of uranyl, neptunyl, and plutonyl, including the lower stability of Np(VI) and Pu(VI) compared with U(VI).

We report vibrational predissociation spectra of the four protonated dipeptides derived from glycine and sarcosine, GlyGlyH(+)•(H(2))(1,2), GlySarH(+)•(D(2))(2), SarGlyH(+)•(H(2))(2), and SarSarH(+)•(D(2))(2), generated in a cryogenic ion trap. Sharp bands were recovered by monitoring photoevaporation of the weakly bound H(2) (D(2)) molecules in a linear action regime throughout the 700-4200 cm(-1) range using a table-top laser system. The spectral patterns were analyzed in the context of the low energy structures obtained from electronic structure calculations. These results indicate that all four species are protonated on the N-terminus, and feature an intramolecular H-bond involving the amino group. The large blue-shift in the H-bonded N-H fundamental upon incorporation of a methyl group at the N-terminus indicates that this modification significantly lowers the strength of the intramolecular H-bond. Methylation at the amide nitrogen, on the other hand, induces a significant rotation (~110°) about the peptide backbone.

Ion populations formed from electrospray of uranyl nitrate solutions containing different amides vary depending on ligand nucleophilicity and steric crowding at the metal center. The most abundant species were ion pair complexes having the general formula [UO(2)(NO(3))(amide)(n=2,3)](+); however, singly charged complexes containing the amide conjugate base and reduced uranyl UO(2)(+) were also formed as were several doubly charged species. The formamide experiment produced the greatest diversity of species resulting from weaker amide binding, leading to dissociation and subsequent solvent coordination or metal reduction. Experiments using methyl formamide, dimethyl formamide, acetamide, and methyl acetamide produced ion pair and doubly charged complexes that were more abundant and less abundant complexes containing solvent or reduced uranyl. This pattern is reversed in the dimethylacetamide experiment, which displayed lower abundance doubly charged complexes, but augmented reduced uranyl complexes. DFT investigations of the tris-amide ion pair complexes showed that interligand repulsion distorts the amide ligands out of the uranyl equatorial plane and that complex stabilities do not increase with increasing amide nucleophilicity. Elimination of an amide ligand largely relieves the interligand repulsion, and the remaining amide ligands become closely aligned with the equatorial plane in the structures of the bis-amide ligands. The studies show that the phenomenological distribution of coordination complexes in a metal-ligand electrospray experiment is a function of both ligand nucleophilicity and interligand repulsion and that the latter factor begins exerting influence even in the case of relatively small ligands like the substituted methyl-formamide and methyl-acetamide ligands.

There is now strong evidence for the existence of macrocyclic isomers of b(n)(+) ions, the formation and subsequent opening of which can lead to loss of sequence information from protonated peptides in multiple-stage tandem mass spectrometry experiments. In this study, the fragmentation patterns of protonated YARFLG and permuted isomers of the model peptide were investigated by collision-induced dissociation. Of interest was the potential influence of the arginine residue, and its position in the peptide sequence, on formation of the presumed macrocyclic b(5) ion isomer and potential loss of sequence information. We find that regardless of the sequence position (either internal or at the N- or C-terminus), only direct sequence ions or ions directly related to fragmentation of the arginine side chain are observed.