Publications

A catalytic system combining the high activity of homogeneous catalysts and the ease of use of heterogeneous catalysts for methane activation is reported. The vanadium-containing metal-organic frameworks (MOFs) MIL-47 and MOF-48 are found to have high catalytic activity and chemical stability. They convert methane selectively to acetic acid with 70% yield (490 TON) based on K(2)S(2)O(8) as an oxidant. Isotopic labeling experiments showed that two methane molecules are converted to the produced acetic acid. The MOF catalysts are reusable and remain catalytically active for several recycling steps without losing their crystalline structures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Abstract This Letter presents the detection of a source at the position of the Type Ib/c supernova (SN) 2013ge more than four years after the radioactive component is expected to have faded. This source could mark the first post-SN direct detection of a surviving companion to a stripped-envelope Type Ib/c explosion. We test this hypothesis and find the shape of the source’s spectral energy distribution is most consistent with that of a B5 I supergiant. While binary models tend to predict OB-type stars for stripped-envelope companions, the location of the source on a color–magnitude diagram places it redward of its more likely position on the main sequence (MS). The source may be temporarily out of thermal equilibrium, or a cool and inflated non-MS companion, which is similar to the suggested companion of Type Ib SN 2019yvr that was constrained from pre-SN imaging. We also consider other possible physical scenarios for the source, including a fading SN, circumstellar shock interaction, line-of-sight coincidence, and an unresolved host star cluster, all of which will require future observations to more definitively rule out. Ultimately, the fraction of surviving companions (“binary fraction”) will provide necessary constraints on binary evolution models and the underlying physics.

GRB 170519A was discovered by \emph{Swift}/BAT, and then observed by \emph{Swift}/XRT, \emph{Swift}/UVOT, and ground-based telescopes. We report Lick/KAIT observations of GRB 170519A, and make temporal analysis and spectral joint fits of its multiwavelength light curves. The observations present a relatively complete afterglow structure, including two X-ray flares (Flares I and II), optical onset (Slice 1), normal decay (Slices 2 and 3), and a possible jet break. The spectrum of the bright X-ray flare (Flare II) indicates that a thermal component exists at $t = 190$--240~s. \textbf{The blackbody emits in the photospheric radius $R_{\rm ph}\sim 10^{11}$ cm,} and its temperature ($kT$) decreases with time from \textbf{1.08 to 0.37 keV, its Lorentz factor of blackbody ($Γ_{\rm BB}$) decreases with time from 67.71 to 46.70. The luminosity of the blackbody ($L_{\rm BB}$), $kT$ and $Γ_{\rm BB}$ follow the relations $\bf L_{\rm BB} \propto kT^{2.49\pm 0.03}$ and $Γ_{\rm BB}\propto L_{\rm BB}^{0.27}$ (estimated from \cite{fan2012}).} In the optical light curves, there is an onset bump in the early-time afterglow, rising with an index $α_{O,1} \approx -0.43$ and peaking $\sim1174.9$ s since the BAT trigger. The bump then decays with $\bf α_{O,2} \approx 0.88$ in the normal decay phase, and the X-ray flux decays with a similar index of $\bf α_{X,1} \approx 0.95$. There is no obvious spectral evolution in the normal decay phases, with photon index $\hatΓ = 1.86$ and 1.92 in Slices 2 and 3, respectively. We find that the multiwavelength light curves of the GRB 170519A afterglow can be well fitted by an external shock with time-dependent $ε_B$. In the early afterglow, the value of $ε_B$ decays rapidly from $\bf 4.29\times10^{-2}$ to $\bf 8.23\times10^{-3}$.

Terminal alkenes are easily derivatized, making them desirable functional group targets for polyketide synthase (PKS) engineering. However, they are rarely encountered in natural PKS systems. One mechanism for terminal alkene formation in PKSs is through the activity of an acyl-CoA dehydrogenase (ACAD). Herein, we use biochemical and structural analysis to understand the mechanism of terminal alkene formation catalyzed by an γ,δ-ACAD from the biosynthesis of the polyketide natural product FK506, TcsD. While TcsD is homologous to canonical α,β-ACADs, it acts regioselectively at the γ,δ-position and only on α,β-unsaturated substrates. Furthermore, this regioselectivity is controlled by a combination of bulky residues in the active site and a lateral shift in the positioning of the FAD cofactor within the enzyme. Substrate modeling suggests that TcsD utilizes a novel set of hydrogen bond donors for substrate activation and positioning, preventing dehydrogenation at the α,β position of substrates. From the structural and biochemical characterization of TcsD, key residues that contribute to regioselectivity and are unique to the protein family were determined and used to identify other putative γ,δ-ACADs that belong to diverse natural product biosynthetic gene clusters. These predictions are supported by the demonstration that a phylogenetically distant homologue of TcsD also regioselectively oxidizes α,β-unsaturated substrates. This work exemplifies a powerful approach to understand unique enzymatic reactions and will facilitate future enzyme discovery, inform enzyme engineering, and aid natural product characterization efforts.