Publications

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.

HST WFPC2 images are presented that span the inner 19 kpc diameter of the edge-on spiral galaxy NGC 3079; they are combined with ground-based Halpha+[N II] Fabry-Perot spectra and VLA images of radio polarization vectors and rotation measures. Ionized gas filaments within 9 kpc diameter project ~3 kpc above the disk, with the brightest forming the 1 kpc diameter superbubble. They are often resolved into strands ~0."3 (25 pc) wide which emerge from the nuclear CO ring as five distinct gas streams with velocity gradients and dispersions of hundreds of km/s. One stream flows for 250 pc and aligns with the VLBI-scale radio jet, the other four are not connected to the jet, instead curving to the vertical 0.6 kpc above the galaxy disk, then dispersing in a spray of droplets each with ionized mass ~1000 sqrt(f) Msun (volume filling factor f > 0.003 from our data). Shredded clumps of disk gas form a similar structure in hydro models of a galaxy-scale wind. The pattern of magnetic fields and the gas kinematics also suggest a wind of mechanical luminosity 10^43 erg/s that has stagnated in the galaxy disk at radius ~800 pc, flared to larger radii with increasing height as the balancing ISM pressure reduces above the disk, and entrained dense clouds into a vortex. Total KE and momentum of the filaments are (0.4-5)x10^55 sqrt(f) ergs and (1.6-6)x10^47 sqrt(f) dyne s. A star-forming complex elsewhere in the galaxy shows a striking spray of linear filaments that extend for hundreds of parsecs.

Herein we report the synthesis of cation-disordered rocksalt NaMO<sub>2</sub> (M = 3d transition metal), i.e., NaFeO<sub>2–δ</sub> (δ ~ 0.18), for the first time via a martensitic-like phase transformation from β-NaFeO<sub>2</sub>. This disordered rocksalt NaFeO<sub>2–δ</sub> does not exhibit long-range cation ordering, as evidenced by synchrotron X-ray diffraction, neutron diffraction, and transmission electron microscopy analyses. Pair distribution function analysis revealed that although the cation sublattice mostly preserved the rocksalt symmetry, O atoms were significantly displaced to accommodate the different Na<sup>+</sup>–O, Fe<sup>2+</sup>–O, and Fe<sup>3+</sup>–O bond lengths (~2.4, 2.1, and 2 Å, respectively). In addition, we confirmed the presence of O vacancies and partial Fe reduction from 3+ to 2+ in NaFeO<sub>2–δ</sub> based on <sup>57</sup>Fe Mössbauer and X-ray absorption spectroscopy analyses. Controlled experiments revealed that three factors are essential for the successful synthesis of the rocksalt structure: (1) an appropriate precursor structure, (2) the application of a large stress by high-energy milling, and (3) the creation of O vacancies via carbon reduction. Density functional theory calculations demonstrated that these factors substantially affect the energetics of the minimum-energy reaction path of the phase transformation, making the highly metastable disordered rocksalt phase accessible. Our work suggests the effectiveness of mechanical milling to access metastable phases that are structurally related to the precursors via a shearing transformation. Utilizing this mechanism, we were able to predict and synthesize another cation-disordered rocksalt structure, NaMnO<sub>2</sub>, and explain the syntheses of several other related materials.

Open-world instance segmentation is the task of grouping pixels into object instances without any pre-determined taxonomy. This is challenging, as state-of-the-art methods rely on explicit class semantics obtained from large labeled datasets, and out-of-domain evaluation performance drops significantly. Here we propose a novel approach for mask proposals, Generic Grouping Networks (GGNs), constructed without semantic supervision. Our approach combines a local measure of pixel affinity with instance-level mask supervision, producing a training regimen designed to make the model as generic as the data diversity allows. We introduce a method for predicting Pairwise Affinities (PA), a learned local relationship between pairs of pixels. PA generalizes very well to unseen categories. From PA we construct a large set of pseudo-ground-truth instance masks; combined with human-annotated instance masks we train GGNs and significantly outperform the SOTA on open-world instance segmentation on various benchmarks including COCO, LVIS, ADE20K, and UVO.

Anti-Markovnikov additions to alkenes have been a longstanding goal of catalysis, and anti-Markovnikov addition of arenes to alkenes would produce alkylarenes that are distinct from those formed by acid-catalyzed processes. Existing hydroarylations are either directed or occur with low reactivity and low regioselectivities for the linear alkylarene. Herein, we report the first undirected hydroarylation of unactivated alkenes with unactivated arenes that occurs with high regioselectivity for the anti-Markovnikov product. The reaction occurs with a Ni catalyst ligated by a highly sterically hindered N-heterocyclic carbene (NHC, L4 or L5). Catalytically relevant arene- and alkene-bound Ni complexes have been characterized, and the rate-limiting step was shown to be reductive elimination to form the C-C bond. DFT calculations, combined with energy decomposition analysis (EDA), suggest that the difference in activity between catalysts containing large and small carbenes results more from stabilizing intramolecular, non-covalent interactions in the secondary coordination sphere than from steric hindrance.

We propose a new approach for vision based longitudinal and lateral vehicle control. The novel feature of this approach is the use of binocular vision. We integrated two modules consisting of a new, domain-specific binocular stereo algorithm, and a lane marker detection algorithm, and show that the integration results in improved performance for each of the modules. Longitudinal control is supported by detecting and measuring the distances to leading vehicles using binocular stereo. The knowledge of the camera geometry with respect to the locally planar road is used to map the images of the road plane in the two camera views into alignment. This allows us to separate image features into those lying in the road plane, e.g. lane markers, and those due to other objects which are dynamically integrated into an obstacle map. Therefore, in contrast with the previous work, we can cope with the difficulties arising from occlusion of lane markers by other vehicles. Detected vehicles are then tracked in time using a vehicle centered coordinate system. Multiple cameras can be integrated to provide full surround awareness. The detection and measurement of the lane markers provides us with the positional parameters and the road curvature which are needed for lateral vehicle control. Moreover, this information is also used to update the camera geometry with respect to the road, therefore allowing us to cope with the problem of vibrations and road inclination to obtain consistent results from binocular stereo.

An imbalance between triacylglycerol synthesis and breakdown is necessary for the development of obesity. The direct precursor for triacylglycerol biosynthesis is alpha-glycerol phosphate, which can have glycolytic and glyceroneogenic origins. We present a technique for determining the relative glyceroneogenic contribution to triacylglyceride glycerol by labeling the glycerol moiety with 2H2O. The number of hydrogen atoms (n) incorporated from H2O into C-H bonds reflects the metabolic source of alpha-glycerol phosphate and can be calculated by combinatorial analysis of the distribution of mass isotopomers in triacylglyceride glycerol. Three physiological settings with potential effects on glyceroneogenesis and glycolysis were studied in rodents. Adipose tissue acylglyceride glycerol in mice fed a low carbohydrate diet had significantly higher values of n than in mice fed a high carbohydrate diet, suggesting an increased contribution from glyceroneogenesis of from 17 to 50% on the low carbohydrate diet. Similarly, mice administered rosiglitazone had a significant relative increase in glyceroneogenesis (from 17 to 53%), indicated by an increase in adipose acylglyceride glycerol n. Fructose infusion in overnight fasted rats rapidly lowered plasma triacylglyceride glycerol n, reflecting a decreased contribution from glyceroneogenesis (from 66 to 34%) presumably because of increased glycolytic input. In conclusion, we demonstrate that the number of C-H atoms derived from cellular H2O in triacylglyceride glycerol is an informative indicator of alpha-glycerol phosphate origin and, ultimately, triacylglycerol metabolism. Under certain physiological conditions, glyceroneogenesis can be up-regulated in adipose (e.g. low carbohydrate diet) or down-regulated in liver (e.g. fructose infusion). Additionally, stimulation of glyceroneogenesis by rosiglitazone in adipose tissue may be an important factor in the antilipolytic actions of thiazolidinediones.

Abstract Saccharomyces cerevisiae utilizes several regulatory mechanisms to maintain tight control over the intracellular level of farnesyl diphosphate (FPP), the central precursor to nearly all yeast isoprenoid products. High‐level production of non‐native isoprenoid products requires that FPP flux be diverted from production of sterols to the heterologous metabolic reactions. To do so, expression of the gene encoding squalene synthase ( ERG9 ), the first committed step in sterol biosynthesis, was down‐regulated by replacing its native promoter with the methionine‐repressible MET3 promoter. The intracellular levels of FPP were then assayed by expressing the gene encoding amorphadiene synthase ( ADS ) and converting the FPP to amorphadiene. Under certain culture conditions amorphadiene production increased fivefold upon ERG9 repression. With increasing flux to amorphadiene, squalene and ergosterol production each decreased. The levels of these three metabolites were dependent not only upon the level of ERG9 repression, but also the timing of its repression relative to the induction of ADS and genes responsible for enhancing flux to FPP. Biotechnol. Bioeng. 2008;99: 371–378. © 2007 Wiley Periodicals, Inc.

We report a scalably synthesized WO3/BiVO4 core/shell nanowire photoanode in which BiVO4 is the primary light-absorber and WO3 acts as an electron conductor. These core/shell nanowires achieve the highest product of light absorption and charge separation efficiencies among BiVO4-based photoanodes to date and, even without an added catalyst, produce a photocurrent of 3.1 mA/cm2 under simulated sunlight and an incident photon-to-current conversion efficiency of ∼60% at 300–450 nm, both at a potential of 1.23 V versus RHE.