327 research outputs found

    Efficient syntheses of climate relevant isoprene nitrates and (1R,5S)-(−)-myrtenol nitrate

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    Here we report the chemoselective synthesis of several important, climate relevant isoprene nitrates using silver nitrate to mediate a ’halide for nitrate’ substitution. Employing readily available starting materials, reagents and Horner–Wadsworth–Emmons chemistry the synthesis of easily separable, synthetically versatile ‘key building blocks’ (E)- and (Z)-3-methyl-4-chlorobut-2-en-1-ol as well as (E)- and (Z)-1-((2-methyl-4-bromobut-2-enyloxy)methyl)-4-methoxybenzene has been achieved using cheap, ’off the shelf’ materials. Exploiting their reactivity we have studied their ability to undergo an ‘allylic halide for allylic nitrate’ substitution reaction which we demonstrate generates (E)- and (Z)-3-methyl-4-hydroxybut-2-enyl nitrate, and (E)- and (Z)-2-methyl-4-hydroxybut-2-enyl nitrates (‘isoprene nitrates’) in 66–80% overall yields. Using NOESY experiments the elucidation of the carbon–carbon double bond configuration within the purified isoprene nitrates has been established. Further exemplifying our ‘halide for nitrate’ substitution chemistry we outline the straightforward transformation of (1R,2S)-(−)-myrtenol bromide into the previously unknown monoterpene nitrate (1R,2S)-(−)-myrtenol nitrate

    Measurement of isoprene nitrates by GCMS

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    According to atmospheric chemistry models, isoprene nitrates play an important role in determining the ozone production efficiency of isoprene; however this is very poorly constrained through observations as isoprene nitrates have not been widely measured. Measurements have been severely restricted largely due to a limited ability to measure individual isoprene nitrate isomers. An instrument based on gas chromatography/mass spectrometry (GCMS) and the associated calibration methods are described for the speciated measurements of individual isoprene nitrate isomers. Five of the primary isoprene nitrates which formed in the presence of NOx by reaction of isoprene with the hydroxyl radical (OH) in the Master Chemical Mechanism are identified using known isomers on two column phases and are fully separated on the Rtx-200 column. Three primary isoprene nitrates from the reaction of isoprene with the nitrate radical (NO3) are identified after synthesis from the already identified analogous hydroxy nitrate. A Tenax adsorbent-based trapping system allows the analysis of the majority of the known hydroxy and carbonyl primary isoprene nitrates, although not the (1,2)-IN isomer, under field-like levels of humidity and showed no impact from typical ambient concentrations of NOx and ozone

    D=3, N=8 conformal supergravity and the Dragon window

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    We give a superspace description of D=3, N=8 supergravity. The formulation is off-shell in the sense that the equations of motion are not implied by the superspace constraints (but an action principle is not given). The multiplet structure is unconventional, which we connect to the existence of a "Dragon window", that is modules occurring in the supercurvature but not in the supertorsion. According to Dragon's theorem this cannot happen above three dimensions. We clarify the relevance of this window for going on the conformal shell, and discuss some aspects of coupling to conformal matter.Comment: plain tex, 24 pp v2: minor change

    Upper-rim functionalised calix[4]arenes for chemoselective Au3+ detection

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    A unique, readily synthesised, upper-rim 1,3-difunctionalised calix[4]arene is reported; equipped with a fluorophore and an alkyne it mediates the efficient chemoselective detection of Au3+. Its ability to detect Au3+ is not perturbed by Au+ or excess competing and or contaminating metal e.g. platinum, cadmium, mercury, silver, sodium, magnesium or potassium cations

    Three-dimensional topologically gauged N=6 ABJM type theories

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    In this paper we construct the N=6\mathcal N=6 conformal supergravity in three dimensions from a set of Chern-Simons-like terms one for each of the graviton, gravitino, and R-symmetry gauge field and then couple this theory to the N=6\mathcal N=6 superconformal ABJM theory. In a first step part of the coupled Lagrangian for this topologically gauged ABJM theory is derived by demanding that all terms of third and second order in covariant derivatives cancel in the supersymmtry variation of the Lagrangian. To achieve this the transformation rules of the two separate sectors must be augmented by new terms. In a second step we analyze all terms in ÎŽL\delta L that are of first order in covariant derivatives. The cancelation of these terms require additional terms in the transformation rules as well as a number of new terms in the Lagrangian. As a final step we check that all remaining terms in ÎŽL\delta L which are bilinear in fermions cancel which means that the presented Lagrangian and transformation rules constitute the complete answer. In particular we find in the last step new terms in the scalar potential containing either one or no structure constant. The non-derivative higher fermion terms in ÎŽL\delta L that have not yet been completely analyzed are briefly discussed.Comment: 26 pages, v.2 minor corrections, comment on relation to chiral gravity added

    Unifying N=5 and N=6

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    We write the Lagrangian of the general N=5 three-dimensional superconformal Chern-Simons theory, based on a basic Lie superalgebra, in terms of our recently introduced N=5 three-algebras. These include N=6 and N=8 three-algebras as special cases. When we impose an antisymmetry condition on the triple product, the supersymmetry automatically enhances, and the N=5 Lagrangian reduces to that of the well known N=6 theory, including the ABJM and ABJ models.Comment: 19 pages. v2: Published version. Minor typos corrected, references adde

    “Dial Up and Lock In”: Asymmetric organo-Brþnsted acid catalysis incorporating stable isotopes

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    An operationally simple organo-BrĂžnsted-acid-catalyzed asymmetric and regioselective “dial up and lock in” of one or more stable isotopes into organic compounds is unknown. Here, we describe a newly designed, chemically versatile protocol mediating single- or multiple-isotope incorporation into aziridines via a one-pot, three-component, two-step process. By exploiting easy-to-generate isotope-derived starting materials, it allows complete control of isotope positioning, affords >95 atom % isotope incorporation, and generates cis-aziridines with excellent optical activities and regioselectivities. Demonstrating a “low entry point,” and thus easy access to a broad range of researchers, it requires no specialist laboratory equipment and employs readily attainable reaction conditions. Demonstrating their utility, the aziridines are easily transformed into sought-after chiral non-racemic α-amino acids appended with one to three (or more) identical or different isotopes. The widespread use of these compounds ensures that our methodology will be of interest to biological, medicinal, pharmaceutical, agrochemical, biotechnology, materials, and process chemists alike

    The BLG Theory in Light-Cone Superspace

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    The light-cone superspace version of the d=3, N=8 superconformal theory of Bagger, Lambert and Gustavsson (BLG) is obtained as a solution to constraints imposed by OSp(2,2|8) superalgebra. The Hamiltonian of the theory is shown to be a quadratic form of the dynamical supersymmetry transformation.Comment: 45 pages, v2: reference added, minor typos corrected, published versio

    Flux compactification on smooth, compact three-dimensional toric varieties

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    Three-dimensional smooth, compact toric varieties (SCTV), when viewed as real six-dimensional manifolds, can admit G-structures rendering them suitable for internal manifolds in supersymmetric flux compactifications. We develop techniques which allow us to systematically construct G-structures on SCTV and read off their torsion classes. We illustrate our methods with explicit examples, one of which consists of an infinite class of toric CP^1 bundles. We give a self-contained review of the relevant concepts from toric geometry, in particular the subject of the classification of SCTV in dimensions less or equal to 3. Our results open up the possibility for a systematic construction and study of supersymmetric flux vacua based on SCTV.Comment: 27 pages, 10 figures; v2: references, minor typos & improvement
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