Publications

ABSTRACT Organophosphate compounds, which are widely used as pesticides and chemical warfare agents, are cholinesterase inhibitors. These synthetic compounds are resistant to natural degradation and threaten the environment. We constructed a strain of Pseudomonas putida that can efficiently degrade a model organophosphate, paraoxon, and use it as a carbon, energy, and phosphorus source. This strain was engineered with the pnp operon from Pseudomonas sp. strain ENV2030, which encodes enzymes that transform p -nitrophenol into β-ketoadipate, and with a synthetic operon encoding an organophosphate hydrolase (encoded by opd ) from Flavobacterium sp. strain ATCC 27551, a phosphodiesterase (encoded by pde ) from Delftia acidovorans , and an alkaline phosphatase (encoded by phoA ) from Pseudomonas aeruginosa HN854 under control of a constitutive promoter. The engineered strain can efficiently mineralize up to 1 mM (275 mg/liter) paraoxon within 48 h, using paraoxon as the sole carbon and phosphorus source and an inoculum optical density at 600 nm of 0.03. Because the organism can utilize paraoxon as a sole carbon, energy, and phosphorus source and because one of the intermediates in the pathway ( p -nitrophenol) is toxic at high concentrations, there is no need for selection pressure to maintain the heterologous pathway.

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 Detailed spectropolarimetric studies may hold the key to probing the explosion mechanisms and the progenitor scenarios of Type Ia supernovae (SNe Ia). We present multi-epoch spectropolarimetry and imaging polarimetry of SN 2019ein, an SN Ia showing high expansion velocities at early phases. The spectropolarimetry sequence spans from ∼−11 to +10 d relative to peak brightness in the B band. We find that the level of the continuum polarization of SN 2019ein, after subtracting estimated interstellar polarization, is in the range 0.0–0.3 per cent, typical for SNe Ia. The polarization position angle remains roughly constant before and after the SN light-curve peak, implying that the inner regions share the same axisymmetry as the outer layers. We observe high polarization (∼1 per cent) across both the Si ii λ6355 and Ca ii near-infrared triplet features. These two lines also display complex polarization modulations. The spectropolarimetric properties of SN 2019ein rule out a significant departure from spherical symmetry of the ejecta for up to a month after the explosion. These observations disfavour merger-induced and double-detonation models for SN 2019ein. The imaging polarimetry shows weak evidence for a modest increase in polarization after ∼20 d since the B-band maximum. If this rise is real and is observed in other SNe Ia at similar phases, we may have seen, for the first time, an aspherical interior similar to what has been previously observed for SNe IIP. Future polarization observations of SNe Ia extending to post-peak epochs will help to examine the inner structure of the explosion.

The asymmetric intramolecular hydroamination of allenes catalyzed by phosphinegold(I)−bis-p-nitrobenzoate complexes is described. This reaction is applicable to the enantioselective formation of vinyl pyrrolidines and piperidines in 70−99% ee.

Abstract This is the first report of a metal‐free catalytic asymmetric 1,4‐fluoroamination of conjugated dienes.

Abstract Engineered polyketide synthases (PKSs) are promising synthetic biology platforms for the production of chemicals with diverse applications. The dehydratase (DH) domain within modular type I PKSs generates an α,β-unsaturated bond in nascent polyketide intermediates through a dehydration reaction. Several crystal structures of DH domains have been solved, providing important structural insights into substrate selection and dehydration. Here, we present two DH domain structures from two chemically diverse PKSs. The first DH domain, isolated from the third module in the borrelidin PKS, is specific towards a trans-cyclopentane-carboxylate-containing polyketide substrate. The second DH domain, isolated from the first module in the fluvirucin B1 PKS, accepts an amide-containing polyketide intermediate. Sequence-structure analysis of these domains, in addition to previously published DH structures, display many significant similarities and key differences pertaining to substrate selection. The two major differences between BorA DH M3, FluA DH M1 and other DH domains are found in regions of unmodeled residues or residues containing high B-factors. These two regions are located between α3–β11 and β7–α2. From the catalytic Asp located in α3 to a conserved Pro in β11, the residues between them form part of the bottom of the substrate-binding cavity responsible for binding to acyl-ACP intermediates.

We combine the results from several HST investigations of the central structure of early-type galaxies to generate a large sample of parameterized surface photometry. The studies included were those that used the "Nuker law" to characterize the inner light distributions of the galaxies. The sample comprises WFPC1 and WFPC2 V band observations published earlier by our group, R band WFPC2 photometry of Rest et al., NICMOS H band photometry by Ravindranath et al. and Quillen et al., and the BCG WFPC2 I band photometry of Laine et al. The distribution of the logarithmic slopes of the central profiles strongly affirms that the central structure of elliptical galaxies with Mv < -19 is bimodal, based on both parametric and non-parametric analysis. At the HST resolution limit, most galaxies are either power-law systems, which have steep cusps in surface brightness, or core systems, which have shallow cusps interior to a steeper envelope brightness distribution. A rapid transition between the two forms occurs over the luminosity range -22 < Mv < -20, with cores dominating at the highest luminosities, and power-laws at the lowest. There are a few "intermediate" systems that have both cusp slopes and total luminosities that fall within the core/power-law transition, but they are rare and do not fill in the overall bimodal distribution of cusp slopes. These results are inconsistent with the Ferrarese et al. Virgo Cluster Survey (VCS) analysis. However, using galaxies common to the VCS samples, we demonstrate that the VCS models of the cusps are either a poor match to the observations or consist of forms fitted to the galaxy envelopes and extrapolated inward to the HST resolution limit.

Photometric and spectroscopic data of the energetic Type Ic supernova (SN) 2002ap are presented, and the properties of the SN are investigated through models of its spectral evolution and its light curve. The SN is spectroscopically similar to the hypernova SN 1997ef. However, its kinetic energy [~(4-10) ? 1051 ergs] and the mass ejected (2.5-5 M?) are smaller, resulting in a faster evolving light curve. The SN synthesized ~0.07 M? of 56Ni, and its peak luminosity was similar to that of normal SNe. Brightness alone should not be used to define a hypernova, whose defining character, namely very broad spectral features, is the result of high kinetic energy. The likely main-sequence mass of the progenitor star was 20-25 M?, which is also lower than that of both hypernovae SN 1997ef and SN 1998bw. SN 2002ap appears to lie at the low-energy and low-mass end of the hypernova sequence as it is known so far. Observations of the nebular spectrum, which is expected to dominate by the summer of 2002, are necessary to confirm these values.

Single-phase face-centered cubic (fcc) high/medium-entropy alloys (H/MEAs) exhibit a much higher tendency to form nanoscale deformation twins than conventional fcc metals with similar low stacking fault energies (SFEs). This extraordinary propensity for nanotwin formation in H/MEAs cannot therefore be explained by their low SFEs alone. Here, using in situ compression tests of CrCoNi in comparison with Ag nanopillars inside a transmission electron microscope, we found that in the CrCoNi MEA, a high density of nanoscale twins continuously formed with an average thickness of 4.6 nm. In contrast, for similar experiments on Ag with almost identical SFE, following the nucleation of a few twins, they could further thicken to above one hundred nanometers by twin boundary migration. Molecular dynamics calculations indicated that in the highly-concentrated CrCoNi solid solution, the magnitude of the energy barriers for nucleating a stacking fault as a twin precursor in the pristine lattice and for the thickening of an existing twin both span a wide range and largely overlap with each other. Therefore, twin thickening through successive addition of atomic layers is prone to discontinuation, giving way to the nucleation of new twins at other sites where a lower energy barrier is encountered for partial-dislocation mediated fault formation.

Although aluminosilicates and metal phosphates can form porous open-framework materials such as zeolites, sulfide analogs usually form high-density phases because of the relatively small tetrahedral angle at sulfur atoms. One strategy to overcome this limitation is to use tetrahedral clusters as the building blocks to achieve porous sulfide-based networks. The preparation and crystal structures of two indium sulfide open frameworks (ASU-31 and ASU-32) built of supertetrahedral clusters around organic template and water guests are described. ASU-31, based on the sodalite-tetrahedrite network, contains cavities 25.6 angstroms in diameter, and ASU-32, based on the tetragonal CrB 4 network, contains channels with a minimum diameter of 14.7 angstroms. The organic cations can be completely exchanged with sodium ions in aqueous solution at room temperature without degradation of the crystals.

We have systematically measured the room-temperature thermal conductivity of epitaxial layers of InxGa1−xN alloys with 15 different Indium compositions ranging from 0.08 to 0.98 by time-domain thermoreflectance method. The data are compared to the estimates of the strength of phonon scattering by cation disorder. The thermal conductivity is in good agreement with the theoretical modeling results based on the mass difference for In-rich (x &amp;gt; 0.9) and Ga-rich (x &amp;lt; 0.2) compositions. At intermediate compositions (0.2 &amp;lt; x &amp;lt; 0.9), the thermal conductivity is strongly suppressed below the values expected for homogeneous alloys. We attribute this suppression of thermal conductivity to phonon scattering by nanometer-scale compositional inhomogeneities in alloys.