Mechanistic Studies of Diastereomeric Nickel(II)<i>N</i>-Glycoside Complexes Using Tandem Mass Spectrometry

and, Glenn Smith; Leary, Julie A.

doi:10.1021/ja9814319

Cited by 51 publications

(47 citation statements)

References 57 publications

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“…All Zn-coordinating bond lengths were between 1.98 -2.19 Å. The monosaccharide ring conformation was found to occupy the 4 C 1 conformation, which was previously observed in theoretical calculations of Ni(II)/diaminopropane/glucose complexes [32]. Structure Glc7 exhibited a theoretical cross section of 100.0 Å 2 which deviates 1.2% from the experimental cross section.…”

Section: Resultssupporting

confidence: 60%

“…Previous studies have shown that synthesis of N-glycosides of this type yield specifically the beta-anomer [36]. While the 4 C 1 conformation is known to be the lowest energy conformation of monosaccharides [37], previous DFT calculations of these complexes observed twist boat geometries as well [32]. A total of 29 initial geometries were generated allowing the coordination of the metal center to each m/z 364 3 328…”

Section: Resultsmentioning

confidence: 99%

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Conformational studies of Zn-Ligand-Hexose diastereomers using ion mobility measurements and density functional theory calculations

Leavell

Gaucher

Leary

et al. 2002

J. Am. Soc. Mass Spectrom.

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Ion mobility studies and density functional theory calculations were used to study the structures of [Zn/diethylenetriamine/Hexose/Cl] ϩ complexes in an effort to probe differences in the three-dimensional conformations. This information allows us to gain insight into the structure of these complexes before collisional activation, which is the first step in understanding the stereoselective dissociations observed under collisionally activated conditions. The collision cross sections obtained from the ion mobility measurements showed that the mannose structure is more compact than the galactose and glucose complexes, respectively. Using density functional theory, candidate structures for each of the experimentally observed complexes were generated. Two criteria were used to determine the most likely structures of these complexes before activation: (1) The allowed relative energies of the molecules (between 0 -90 kJ/mol) and (2) collision cross section agreement (within 2%) between the theoretically determined structures and the experimentally determined cross section. It was found that the identity of the monosaccharide made a difference in the overall conformation of the metal-ligand-monosaccharide complex. For glucose and galactose, metal coordination to O(6) was found to be favorable, with the monosaccharide occupying the 4 C 1 chair conformation, while for mannose, O(2) metal coordination was found with the monosaccharide in a B 3,0 conformation. Coordination numbers varied between four and six for the Zn(II) metal centers. Given these results, it appears that the stereochemistry of the monosaccharide influences the conformation and metal coordination sites of the Zn(II)/monosaccharide/dien complex. These differences may influence the dissociation products observed under collisionally activated conditions. (J Am Soc Mass Spectrom 2002, 13, 284 -293) © 2002 American Society for Mass Spectrometry T he use of ion mobility mass spectrometry (IMMS), in combination with theoretical methods to gain insight into the gas phase 3-dimensional structure of biomolecules, is now a well established technique [1][2][3][4][5][6][7]. Numerous examples of these types of studies can be found in the literature. For example, the conformation of peptide ions has been examined to determine how the gas phase structure mimics the solution phase structure [3], or how the substitution of different metal ions for protons affects the overall conformation of peptide chains [4]. Simple amino acids have been investigated by IMMS to determine if they are zwitterions in the gas phase as in solution [5]. IMMS has also been used as a technique to separate opiates and opiate metabolites [6] or even peptide mixtures [7].In this study, the gas phase structures of the three biologically relevant monosaccharides complexed with Zn(II)/diethylenetriamine are explored in an effort to probe the conformational differences among the complexes. The information gained aids the understanding of the coordination sites of metal ions to monosaccharides, and help...

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Section: Resultssupporting

confidence: 60%

Section: Resultsmentioning

confidence: 99%

Conformational studies of Zn-Ligand-Hexose diastereomers using ion mobility measurements and density functional theory calculations

Leavell

Gaucher

Leary

et al. 2002

J. Am. Soc. Mass Spectrom.

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“…and mannose isotopologues revealed that the C 2 H 4 O 2 loss indeed is a superposition of two different cross-ring cleavages that involve either C-5 and C-6 or C-4 and C-5 (Smith & Leary, 1998). Several different mechanism can account for the observed fragmentations (Scheme 11).…”

Section: Molecular Recognition and Supramolecular Chemistrymentioning

confidence: 99%

Molecular recognition and supramolecular chemistry in the gas phase

Schalley

2001

Mass Spectrometry Reviews

289

178

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Supramolecular chemistry, in particular, the fields of molecular recognition and self-assembly, profit much from the development of soft ionization techniques and advanced methods for mass analysis and gas-phase chemistry. Vice versa, weakly bonded architectures and host-guest complexes represent a veritable challenge for the mass spectrometrist, leading to further development of methods and techniques. This review describes the state-of-the-art in this field, and includes topics such as the effects of solvation on meta binding to crown ethers, chiral discrimination of guests by chiral hosts, the elucidation of the secondary structure of self assembled complexes, and the mechanistic pathways of self assembly or the fragmentations of supramolecular complexes in the gas phase.

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“…To date, the vast majority of ion-molecule interaction studies performed by mass spectrometry focus on positive ion studies of cationic adduct species, especially protonated molecules [14] and alkali metal adducts [18 -21]. Dication adduct species, such as alkaline earth metal [22] and transition metal [23] adducts of oligosaccharides have also been explored. Small inorganic anions attaching to neutral analyte molecules, on the other hand, have received far less research attention.…”

mentioning

confidence: 99%

Evaluation of the role of multiple hydrogen bonding in offering stability to negative ion adducts in electrospray mass spectrometry

Cai

Concha

Murray

et al. 2002

J. Am. Soc. Mass Spectrom.

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An experimental approach, electrospray mass spectrometry (ES-MS), and a theoretical approach employing computer modeling, have been used to characterize the interaction between small inorganic anions and neutral analyte molecules that form anionic adduct species in negative mode ES mass spectrometry. Certain anionic adducts of small saccharides (e.g., ␣-D-glucose, sucrose) have shown exceptional stability in ES mass spectra even when internal energies are raised at high "cone" voltages. Computer modeling studies reveal that multiple hydrogen bonding strengthens the interaction between these neutral molecules and the attaching anion. The equilibrium structures and stabilization energies of these anionic adducts have been evaluated by semi-empirical, ab initio, and density functional theory (DFT) methods. Chloride anion is found to be capable of forming "bridging" hydrogen bonds between monosaccharide rings of polysaccharides resulting in the stabilization of chloride adducts, thus reducing the tendency for the glycosidic bond to decompose. Moreover, the tendency for various hydroxyl hydrogens on saccharide molecules to dissociate in the form of HA ( [5][6][7][8], have been used to generate anionic adducts for ES-MS studies. The formation and decomposition of chloride adducts have been further investigated from a thermodynamic standpoint [9 -12]. However, the conditions that favor the formation and survival of anionic adducts have not been extensively defined and are not fully understood. Moreover, the interactions between neutral analyte molecules and the attaching small inorganic anions have not been fully characterized.Various mass spectrometry methods have been applied to probe the interactions between ions and neutral analyte molecules [13][14][15]. These methods typically evaluate enthalpies of ion-molecule reactions or unimolecular dissociations of ionic adducts to derive gasphase thermodynamic properties such as bond energies and ion affinities. In some cases, the nature of the ion-molecule interaction could be further elucidated by determining the difference in the entropy changes for competing decomposition pathways [16,17]. To date, the vast majority of ion-molecule interaction studies performed by mass spectrometry focus on positive ion studies of cationic adduct species, especially protonated molecules [14] and alkali metal adducts [18 -21]. Dication adduct species, such as alkaline earth metal [22] and transition metal [23] adducts of oligosaccharides have also been explored. Small inorganic anions attaching to neutral analyte molecules, on the other hand, have received far less research attention. However, a few studies employing anion attachment in negative ion ES-MS have appeared, such as reports on iodide attachment to acetone [24], chloride attachment to saccharides [1, 10 -12], and cyanide attachment (including covalent) to fullerenes [6,8]. In order to gain insight into the exact nature of the interactions between neutral analyte molecules and attaching small inorganic anions that are responsi...

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Mechanistic Studies of Diastereomeric Nickel(II)N-Glycoside Complexes Using Tandem Mass Spectrometry

Cited by 51 publications

References 57 publications

Conformational studies of Zn-Ligand-Hexose diastereomers using ion mobility measurements and density functional theory calculations

Conformational studies of Zn-Ligand-Hexose diastereomers using ion mobility measurements and density functional theory calculations

Molecular recognition and supramolecular chemistry in the gas phase

Evaluation of the role of multiple hydrogen bonding in offering stability to negative ion adducts in electrospray mass spectrometry

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