The Supernova Channel of Super-AGB Stars

We study the late evolution of solar metallicity stars in the transition region between white dwarf formation and core collapse. This includes the super-asymptotic giant branch (super-AGB, SAGB) stars, which have massive enough cores to ignite carbon burning and form an oxygen-neon (ONe) core. The most massive SAGB stars have cores that may grow to the Chandrasekhar mass because of continued shell-burning. Their cores collapse, triggering a so called electron capture supernovae (ECSN). From stellar evolution models we find that the initial mass range for SAGB evolution is 7.5 ... 9.25\msun. We perform calculations with three different stellar evolution codes to investigate the sensitivity of this mass range to some of the uncertainties in current stellar models. The mass range significantly depends on the treatment of semiconvective mixing and convective overshooting. To consider the effect of a large number of thermal pulses, as expected in SAGB stars, we construct synthetic SAGB models that include a semi-analytical treatment of dredge-up, hot-bottom burning, and thermal pulse properties. This synthetic model enables us to compute the evolution of the main properties of SAGB stars from the onset of thermal pulses until the core reaches the Chandrasekhar mass or is uncovered by the stellar wind. Thereby, we determine the stellar initial mass ranges that produce ONe-white dwarfs and electron-capture supernovae. The latter is found to be 9.0 ... 9.25\msun for our fiducial model, implying that electron-capture supernovae would constitute about 4% of all supernovae in the local universe. Our synthetic approach allows us to explore the uncertainty of this number imposed by uncertainties in the third dredge-up efficiency and ABG mass loss rate. We find for ECSNe a upper limit of ~20% of all supernovae (abridged).Comment: 13 pages, 16 figures, submitted to ApJ, uses emulateap

Unlocking New Reactivities in Enzymes by Iminium Catalysis

The application of biocatalysis in conquering challenging synthesis requires the constant input of new enzymes. Developing novel biocatalysts by absorbing catalysis modes from synthetic chemistry has yielded fruitful new-to-nature enzymes. Organocatalysis was originally bio-inspired and has become the third pillar of asymmetric catalysis. Transferring organocatalytic reactions back to enzyme platforms is a promising approach for biocatalyst creation. Herein, we summarize recent developments in the design of novel biocatalysts that adopt iminium catalysis, a fundamental branch in organocatalysis. By repurposing existing enzymes or constructing artificial enzymes, various biocatalysts for iminium catalysis have been created and optimized via protein engineering to promote valuable abiological transformations. Recent advances in iminium biocatalysis illustrate the power of combining chemomimetic biocatalyst design and directed evolution to generate useful new-to-nature enzymes

Characterization of Cg10062 from Corynebacterium glutamicum: Implications for the Evolution of cis-3-Chloroacrylic Acid Dehalogenase Activity in the Tautomerase Superfamily†

A 149-amino acid protein designated Cg10062 is encoded by a gene from Corynebacterium glutamicum. The physiological function of Cg10062 is unknown, and the gene encoding this protein has no obvious genomic context. Sequence analysis links Cg10062 to the cis-3-chloroacrylic acid dehalogenase (cis-CaaD) family, one of the five known families of the tautomerase superfamily. The characterized tautomerase superfamily members have two distinctive characteristics: a P-cc-p structure motif and a catalytic amino-terminal proline. Pro-1 is present in the Cg10062 amino acid sequence along with His-28, Arg-70, Arg-73, Tyr-103, and Glu-114, all of which have been implicated as critical residues for cis-CaaD activity. The gene for Cg10062 has been cloned and the protein overproduced, purified, and subjected to kinetic and mechanistic characterization. Like cis-CaaD, Cg10062 functions as a hydratase: it converts 2-oxo-3-pentynoate to acetopyruvate and processes 3-bromopropiolate to a species that inactivates the enzyme by acylation of Pro-1. Kinetic and (1)H NMR spectroscopic studies also show that Cg10062 processes both isomers of 3-chloroacrylic acid at low levels with a clear preference for the cis isomer. Pro-1 is critical for the dehalogenase and hydratase activities because the PIA mutant no longer catalyzes either reaction. The presence of the six key catalytic residues and the hydratase activity coupled with the absence of an efficient cis-CaaD activity and the lack of isomer specificity implicate factors beyond this core set of residues in cis-CaaD catalysis and specificity. This work sets the stage for in-depth mechanistic and structural studies of Cg10062, which could identify the additional features necessary for a fully active and highly specific cis-CaaD. Such results will also shed light on how cis-CaaD emerged in the tautomerase superfamily because Cg10062 could be characteristic of an intermediate along the evolutionary pathway for this dehalogenase

Nucleosynthesis in O-Ne-Mg Supernovae

We have studied detailed nucleosynthesis in the shocked surface layers of an Oxygen-Neon-Magnesium core collapse supernova with an eye to determining if the conditions are suitable for r process nucleosynthesis. We find no such conditions in an unmodified model, but do find overproduction of N=50 nuclei (previously seen in early neutron-rich neutrino winds) in amounts that, if ejected, would pose serious problems for galactic chemical evolution.Comment: 12 pages, 1 figure, to be published in Astrophysical Journal Letter

In Situ Acetaldehyde Synthesis for Carboligation Reactions

The enzyme 4-oxalocrotonate tautomerase (4-OT) can promis-cuously catalyze various carboligation reactions using acetalde-hyde as a nucleophile. However, the highly reactive nature ofacetaldehyde requires intricate handling, which can impede itsusage in practical synthesis. Therefore, we investigated threeenzymatic routes to synthesize acetaldehyde in situ in one-potcascade reactions with 4-OT. Two routes afforded practicalacetaldehyde concentrations, using an environmental pollu-tant,trans-3-chloroacrylic acid, or a bio-renewable, ethanol, asstarting substrate. These routes can be combined with 4-OTcatalyzed Michael-type additions and aldol condensations inone pot. This modular systems biocatalysis methodology pro-vides a stepping stone towards the development of larger arti-ficial metabolic networks for the practical synthesis of impor-tant chemical synthons

Enantiocomplementary Michael Additions of Acetaldehyde to Aliphatic Nitroalkenes Catalyzed by Proline‐Based Carboligases

The blockbuster drug Pregabalin is widely prescribed for the treatment of painful diabetic neuropathy. Given the continuous epidemic growth of diabetes, the development of sustainable synthesis routes for Pregabalin and structurally related pharmaceutically active γ-aminobutyric acid (GABA) derivatives is of high interest. Enantioenriched γ-nitroaldehydes are versatile synthons for the production of GABA derivatives, which can be prepared through a Michael-type addition of acetaldehyde to α,β-unsaturated nitroalkenes. Here we report that tailored variants of the promiscuous enzyme 4-oxalocrotonate tautomerase (4-OT) can accept diverse aliphatic α,β-unsaturated nitroalkenes as substrates for acetaldehyde addition. Highly enantioenriched aliphatic ( R )- and ( S )-γ-nitroaldehydes were obtained in good yields using two enantiocomplementary 4-OT variants. Our results underscore the synthetic potential of 4-OT for the preparation of structurally diverse synthons for bioactive analogues of Pregabalin

Thermohaline mixing in low-mass giants: RGB and beyond

Thermohaline mixing has recently been proposed to occur in low mass red giants, with large consequence for the chemical yields of low mass stars. We investigate the role of thermohaline mixing during the evolution of stars between 1 Msun and 3 Msun. We use a stellar evolution code which includes rotational mixing and internal magnetic fields. We confirm that thermohaline mixing has the potential to destroy most of the helium 3 which is produced earlier on the main sequence during the red giant stage, in stars below 1.5Msun. We find this process to continue during core helium burning and beyond. We find rotational and magnetic mixing to be negligible compared to the thermohaline mixing in the relevant layers, even if the interaction of thermohaline motions with the differential rotation may be essential to establish the time scale of thermohaline mixing in red giants.Comment: Proceedings of the Conference "Unsolved problems in stellar physics" - Cambridge, July 200