10 research outputs found

    Characterization of the C3H6O+. ion from 2-methoxyethanol. Mixture analysis by dissociation and neutralization—reionization

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    The C3H6O+. ion formed upon the dissociative ionization of 2-methoxyethanol is identified by a combination of several tandem mass spectrometry methods, including metastable ion (MI) characteristics, collisionally activated dissociation (CAD), and neutralization—reionization mass spectrometry (NRMS). The experimental data conclusively show that 2-methoxyethanol molecular ion, namely, HOCH2CH2OCH3+., loses H2O to yield mainly the distonic radical ion ·CH2CH2OCH2+ along with a smaller amount of ionized methyl vinyl ether, namely, CH2=CHOCH3+.. Ring-closed products, such as the oxetane or the propylene oxide ion are not observed. The proportion of ·CH2CH2OCH2+ increases with decreasing internal energy of the 2-methoxyethanol ion, which indicates a lower critical energy for the pathway leading to this product than for the competitive generation of CH2=CHOCH3+.. The present study also uses MI, CAD, and NRMS data to assess the structure of the distonic ion+ (CH3)CHOCH2 · (ring-opened ionized propylene oxide) and evaluate its isomerization proclivity toward the methyl vinyl ether ion

    Unimolecular Chemistry of Li +

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    The sodium ion affinities of cytosine and its methylated derivatives.

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    International audienceThe sodium ion affinities of cytosine (Cyt), 5-methylcytosine (5MeCyt) and 1-methylcytosine (1MeCyt) have been determined by experimental and quantum chemical methods. Na(+)-bound heterodimers were produced carrying one cytosine or methylated cytosine ligand (designated as C) and one peptide or amino acid reference base (designated as Pep); the Pep molecules included the peptides GlyLeu, GlyPhe, SerGly, and PheGly, and the amino acid His. The dissociation kinetics of these C--Na(+)--Pep ions were determined by collisionally activated dissociation (CAD) and converted to relative and absolute Na(+) affinities via kinetic method approaches. Relative Na(+) affinities increase in the order (kJ/mol): GlyLeu (0) < Cyt (3) < GlyPhe (4) < SerGly (6) < 5MeCyt (8) < PheGly (11) < 1MeCyt (13) < His (17). Anchoring the relative values of the nucleobases to the absolute affinities of the reference bases leads to absolute Na(+) affinities of 214 +/- 8, 219 +/- 8, and 224 +/- 8 kJ/mol for Cyt, 5MeCyt, and 1MeCyt, respectively. Ab initio calculations were used to confirm these results. The computed affinities of Cyt (213 kJ/mol) and 1MeCyt (217 kJ/mol) are in very good agreement with the experiments. These values unambiguously correspond to Na(+) complexes with the keto form of cytosine and its methyl derivatives. Ab initio calculations on tautomerization mechanisms in the gas versus condensed phase are used to discuss why the sodiated keto isomers were formed in the present electrospray ionization (ESI) experiments, but the enol isomers in previous fast atom bombardment (FAB) experiments

    Characterization of linear and branched polyacrylates by tandem mass spectrometry

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    The unimolecular degradation of alkali-metal cationized polyacrylates with the repeat unit CH(2)CH(COOR) and a variety of ester pendants has been examined by tandem mass spectrometry. The fragmentation patterns resulting from collisionally activated dissociation depend sensitively on the size of the ester alkyl substituent (R). With small alkyl groups, as in poly(methyl acrylate), lithiated or sodiated oligomers (M) decompose via free-radical chemistry, initiated by random homolytic C-C bond cleavages along the polymer chain. The radical ions formed this way dissociate further by backbiting rearrangements and beta scissions to yield a distribution of terminal fragments with one of the original end groups and internal fragments with 2-3 repeat units. If the ester alkyl group bears three or more carbon atoms, cleavages within the ester moieties become the predominant decomposition channel. This distinct reactivity is observed if R = t-butyl, n-butyl, or the mesogenic group (CH(2))(11)-O-C(6)H(4)-C(6)H(4)-CN. The [M+alkali metal](+) ions of the latter polyacrylates dissociate largely by charge-remote 1,5-H rearrangements that convert COOR to COOH groups by expulsion of 1-alkenes. The acid groups may displace an alcohol unit from a neighboring ester pendant to form a cyclic anhydride, unless hindered by steric effects. Using atom transfer radical polymerization, hyperbranched polyacrylates were prepared carrying ester groups both within and between the branches. Unique alkenes and alcohols are cleaved from ester groups at the branching points, enabling determination of the branching architecture

    Dimethylcarbene, Its Radical Cation and Dication

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    Threats to an ecosystem service: pressures on pollinators

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    Insect pollinators of crops and wild plants are under threat globally and their decline or loss could have profound economic and environmental consequences. Here, we argue that multiple anthropogenic pressures – including land-use intensification, climate change, and the spread of alien species and diseases – are primarily responsible for insect-pollinator declines. We show that a complex interplay between pressures (eg lack of food sources, diseases, and pesticides) and biological processes (eg species dispersal and interactions) at a range of scales (from genes to ecosystems) underpins the general decline in insect-pollinator populations. Interdisciplinary research on the nature and impacts of these interactions will be needed if human food security and ecosystem function are to be preserved. We highlight key areas that require research focus and outline some practical steps to alleviate the pressures on pollinators and the pollination services they deliver to wild and crop plants
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