327 research outputs found
Efficient syntheses of climate relevant isoprene nitrates and (1R,5S)-(â)-myrtenol nitrate
Here we report the chemoselective synthesis of several important, climate relevant isoprene nitrates using silver nitrate to mediate a âhalide for nitrateâ substitution. Employing readily available starting materials, reagents and HornerâWadsworthâEmmons chemistry the synthesis of easily separable, synthetically versatile âkey building blocksâ (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, âoff the shelfâ materials. Exploiting their reactivity we have studied their ability to undergo an âallylic halide for allylic nitrateâ 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 (âisoprene nitratesâ) in 66â80% overall yields. Using NOESY experiments the elucidation of the carbonâcarbon double bond configuration within the purified isoprene nitrates has been established. Further exemplifying our âhalide for nitrateâ substitution chemistry we outline the straightforward transformation of (1R,2S)-(â)-myrtenol bromide into the previously unknown monoterpene nitrate (1R,2S)-(â)-myrtenol nitrate
Measurement of isoprene nitrates by GCMS
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
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
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
In this paper we construct the 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
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 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 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 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
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
âDial Up and Lock Inâ: Asymmetric organo-BrĂžnsted acid catalysis incorporating stable isotopes
An operationally simple organo-BrĂžnsted-acid-catalyzed asymmetric and regioselective âdial up and lock inâ 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 âlow entry point,â 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
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
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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