Justin Renaud

Experiment and theory combine to produce a practical negative ion calibration set for collision cross‐section determinations by travelling‐wave ion‐mobility mass spectrometry

RATIONALE There are relatively few cross-section measurements for negatively charged ions. Available calibrants provide sufficient cross-section coverage for the 390 Å(2) to 641 Å(2) and 1174 Å(2) to 3395 Å(2) ranges. This is not particularly well suited for determining the collision cross-sections of smaller ions, such as small peptides. METHODS Molecular mechanics/molecular dynamics (MM/MD) simulations, coupled with simulated annealing, were used to find the low-energy molecular conformations of polystyrene (PS) oligomers of length 3-9 (singly deprotonated) and 5-13 (doubly deprotonated). The trajectory method in MOBCAL was employed to derive their respective collision cross-sections, Ω. A calibration plot relating corrected Ω values to drift times in a Waters Synapt G2 mass spectrometer was used to predict the Ω values for the -2 to -6 charge states of dT(10) DNA. RESULTS The in silico design of a reliable negative ion calibration set for ion mobility spectrometry successfully resulted in the use of α,ω-carboxy-terminated PS oligomers to determine the collision cross-sections of negatively charged ions in the range 132-388 Å(2). All charge states of dT(10) DNA were predicted to within 3% of the referenced values for these ions. CONCLUSIONS α,ω-Carboxy-terminated PS oligomers were found to be an excellent choice to calibrate ion mobility spectrometers to obtain cross-sections for moderately sized ions. Oligomers with fewer, or weaker, interactions among the internal side chains (like poly(ethylene glycol) oligomers) tend to have a wide range of low-energy molecular conformations resulting in large standard deviations in their theoretically predicted collision cross-sections.

Old Acid, New Chemistry. Negative Metal Anions Generated from Alkali Metal Oxalates and Others

A brief search in Sci Finder for oxalic acid and oxalates will reward the researcher with a staggering 129,280 hits. However, the generation of alkali metal and silver anions via collision-induced dissociation of the metal oxalate anion has not been previously been reported, though Tian and coworkers recently investigated the dissociation of lithium oxalate [18]. The exothermic decomposition of alkali metal oxalate anion to carbon dioxide in the collision cell of a triple quadrupole mass spectrometer leaves no place for the electron to reside, resulting in a double electron-transfer reaction to produce an alkali metal anion. This reaction is facilitated by the negative electron affinity of carbon dioxide and, as such, the authors believe that metal oxalates are potentially unique in this respect. The observed dissociation reactions for collision with argon gas (1.7−1.8 × 10−3 mbar) for oxalic acid and various alkali metal oxalates are discussed and summarized. Silver oxalate is also included to demonstrate the propensity of this system to generate transition-metal anions, as well.

Reactions of atomic metal anions in the gas phase: competition between electron transfer, proton abstraction and bond activation.

Bare metal anions K(-), Rb(-), Cs(-), Fe(-), Co(-), Ni(-), Cu(-), and Ag(-), generated by electrospray ionization of the corresponding oxalate or tricarballylate solutions, were allowed to react with methyl and ethyl chloride, methyl bromide, nitromethane, and acetonitrile in the collision hexapole of a triple-quadrupole mass spectrometer. Observed reactions include (a) the formation of halide, nitride, and cyanide anions, which was shown to be likely due to the insertion of the metal into the C-X, C-N, and C-C bonds, (b) transfer of H(+) from the organic molecule, which is demonstrated to most likely be due to the simple transfer of a proton to form neutral metal hydride, and (c) in the case of nitromethane, direct electron transfer to form the nitromethane radical anion. Interestingly, Co(-) was the only metal anion to transfer an electron to acetonitrile. Differences in the reactions are related to the differences in electron affinity of the metals and the Δ(acid)H° of the metals and organic substrates. Density functional theory calculations at the B3-LYP/6-311++G(3df,2p)//B3-LYP/6-31+G(d) level of theory shed light on the relative energetics of these processes and the mechanisms by which they take place.

Triacylglycerols and aliphatic alcohols from fruits of three Tunisian Pistacia lentiscus populations.

BACKGROUND The search for other sources of vegetable oils by the exploitation and the enhancement of other oil plants will be needed to meet the demands of the international market. This study aims to determine the triacylglycerol (TAG) molecular species and aliphatic alcohol compositions of unexploited fruits of three Tunisian Pistacia lentiscus (lentisc) populations from the Korbous, Tebaba and Rimel areas of Tunisia. RESULTS Results show that the content of total TAG varies from 738.32 mg g(-1) of total lipid in the Tebaba population to 981.15 mg g(-1) of total lipid in the Korbous population. Furthermore, 14 species of TAG were detected in the three studied populations. In addition, 13 aliphatic compounds were identified and classified into two groups: (1) aliphatic alcohols with fewer than 20 carbon atoms (hexadecanol, heptadecanol, (Z)-octadec-9-en-1-ol, octadecanol and nonadécanol); and (2) the policosanol group (eicosenol, docosenol, docosanol tetracosanol, hexacosanol octacosanol and triacontanol). The Tebaba population showed a distinct composition compared to Korbous and Rimel where heptadecanol is the major compound. CONCLUSION Quantitatively, the most abundant TAG species are those constituted by palmitic, oleic and/or linoleic acid. Furthermore, the significant difference observed at the oil composition is associated with a remarkable station effect.

Variation in oil content, fatty acid and phytosterols profile of Onopordum acanthium L. during seed development

This study has determined oil, fatty acid (FA) and phytosterols content during the ripening of the Tunisian Onopordum acanthium L. seeds. In total, nine FAs and six phytosterols were identified. The main FAs were linoleic acid (0.18–8.06 mg/g of seed) followed by oleic acid (0.051–2.45 mg/g of seed), palmitic acid and stearic acid. Pentadecanoic acid was detected, for the first time, in unripe fruits and the two last stages of development were characterised by a relative abundance of erucic acid. Overall, β-sitosterol (34.5–77.79% of total sterols) was the major 4-desmethylsterols during maturation. The first episodes of growth were characterised by the best amounts of stigmasterol and campesterol, while stigmastanol and Δ7 sitosterol had quoted the semi-ripe and fully ripe fruits; however, cholesterol was absent. These findings are useful in understanding a potential new source of important natural compounds (Phytosterols and USFA) found in this fruit and when harvest should be undertaken to optimise desired FA and phytosterols content.

The applicability of the kinetic method for measuring relative affinities of macromolecules for polyatomic substrates.

This paper is a review of the kinetic method for the determination of thermochemical values for gas-phase molecules. In addition, we have explored the utility of the kinetic method to obtain meaningful relative binding energies of macromolecules for polyatomic substrates using a system comprising poly(methylmethacrylate) (PMMA) oligomers and doubly protonated diaminoalkanes. The major factors which determined the suitability of the kinetic method for this system were identified as (i) the structural arrangement of the parent ion complex, (ii) possible reverse activation barriers and (iii) the evaluations of A(AS‡). Molecular mechanics/molecular dynamics simulations, together with ion mobility spectrometry, suggests the parent ion complexes represent a relatively equal sharing of the substrate between the two PMMA oligomers within the complex and that the two PMMA oligomers interact almost exclusively with the substrate and not with each other. Tandem mass spectrometry of the trimeric parent complexes resulted in one PMMA unit leaving as a neutral which suggests very limited coulombic repulsion (which would contribute to a reverse activation barrier). The drift times of PMMA–diaminoalkane complexes that were generated directly by electrospray ionization mass spectrometry or by dissociation of a trimeric PMMA–diaminoalkane–PMMA complex were found to be identical and when, combined with molecular mechanics/molecular dynamics simulations, suggested that the product PMMA–diaminoalkane dication has the same conformation as it does when part of a trimeric complex. This is evidence for A(AS‡) ≈ A(AS) and using a statistical mechanics approach, A(AS) ≈ 0. The effective temperature variable in the kinetic method expression was found to decrease as a function of the size of the trimeric complex, suggesting that the population distribution of the dissociating ensemble of complexes narrows as size increases.

Structure and Stability of Carbohydrate-Lipid Interactions. Methylmannose Polysaccharide-Fatty Acid Complexes.

We report a detailed study of the structure and stability of carbohydrate–lipid interactions. Complexes of a methylmannose polysaccharide (MMP) derivative and fatty acids (FAs) served as model systems. The dependence of solution affinities and gas‐phase dissociation activation energies (Ea) on FA length indicates a dominant role of carbohydrate–lipid interactions in stabilizing (MMP+FA) complexes. Solution 1H NMR results reveal weak interactions between MMP methyl groups and FA acyl chain; MD simulations suggest the complexes are disordered. The contribution of FA methylene groups to the Ea is similar to that of heats of transfer of n‐alkanes from the gas phase to polar solvents, thus suggesting that MMP binds lipids through dipole‐induced dipole interactions. The MD results point to hydrophobic interactions and H‐bonds with the FA carboxyl group. Comparison of collision cross sections of deprotonated (MMP+FA) ions with MD structures suggests that the gaseous complexes are disordered.