Publications

Wellbeing is shaped by an interplay of genetic and environmental factors and is associated with both health and functioning. It remains unclear whether genetic influences on wellbeing are linked to brain structure and, in turn, early-life psychopathology. Here, we investigated associations between wellbeing polygenic scores (PGS), magnetic resonance imaging (MRI)-derived measures of brain structure, and parent-reported measures of child psychopathology in a large cross-sectional sample of children from the Adolescent Brain Cognitive Development (ABCD) Study (n = 8844; 8.9–11.0 years old). Preregistered analyses revealed no significant associations between wellbeing PGS and regional cortical thickness or subcortical volumes and only a small negative association with surface area of the parahippocampal cortex (ß = -0.03, p = .002), while an exploratory analysis identified a small positive association with intracranial volume (ICV; ß = 0.04, p < .001). Preregistered analyses showed small negative associations between wellbeing PGS and general psychopathology (ß = -0.09, p < .001) and both internalizing (ß = -0.09, p < .001) and externalizing problems (ß = -0.07, p < .001). ICV partially mediated the relationships between wellbeing PGS and psychopathology, accounting for 1.3–3.3 % of these relationships. The findings suggest that while wellbeing PGS have limited associations with regional brain structure in children, they exhibit small protective effects against psychopathology.

Abstract Novel asymmetric 5‐exo‐dig and 5‐endo‐dig cyclizations of silyloxyenynes using palladium and gold complexes are described.

Ni<sub>1–<i>x</i></sub>Fe<sub><i>x</i></sub>OOH thin films prepared via cathodic electrodeposition have been demonstrated to be highly active catalysts for the oxygen evolution reaction (OER) in basic media. Integration of these catalysts with light-absorbing semiconductors is required for photoelectrochemical fuel generation. However, the application of cathodic potentials required for typical electrochemical catalyst deposition limits the library of compatible photoanode materials. Sputter deposition of catalysts circumvents this limitation by enabling facile catalyst layering without cathodic potentials. In this work, we compare the structure and OER activity of sputter-deposited and electrodeposited Ni<sub>1–<i>x</i></sub>Fe<sub><i>x</i></sub>OOH thin films. Electrochemical cycling converts sputtered Ni<sub>1-x</sub>Fe<sub>x</sub> metallic films to the desired oxides/(oxy)hydroxides. Both film preparation methods give catalysts with similar electrochemical behavior across all compositions. Additionally, OER activity is comparable between the deposition methods, with maximum activity for films with ~20% Fe content (320 mV overpotential at j = 10 mA cm<sup>-2</sup> geometric). Electrochemical cycling to convert sputtered metallic Ni<sub>1-x</sub>Fe<sub>x</sub> films to metal oxides/(oxy)hydroxides is found to lower the Fe/Ni ratio, while the electrodeposited films exhibit comparable Fe/Ni ratios before and after electrochemical cycling and characterization. Structurally, Fe is found to incorporate within the Ni(OH)<sub>2</sub>/NiOOH lattice for films formed through both sputter-deposition and electrodeposition. Layered films were also compared to codeposited 1:1 Fe/Ni films. It is found that, for layered films, an Fe top layer inhibits the electrochemical conversion of metallic Ni to Ni(OH)<sub>2</sub>/NiOOH, thus reducing the amount of Ni<sub>1–<i>x</i></sub>Fe<sub><i>x</i></sub>OOH OER-active phase formed. In contrast, migration of metals within Ni-on-top films occurs readily during electrochemical cycling, resulting in films that are structurally and electrochemically indistinguishable from codeposited Ni<sub>1–<i>x</i></sub>Fe<sub><i>x</i></sub>OOH. These findings enable direct application of Ni<sub>1–<i>x</i></sub>Fe<sub><i>x</i></sub>OOH sputtered films to a wider library of photoanodes for light-driven water-splitting applications.

We report the results of a 944 epoch survey for transient sources with archival data from the Very Large Array spanning 22 years with a typical epoch separation of 7 days. Observations were obtained at 5 or 8.4 GHz for a single field of view and achieved a typical point-source detection threshold at the beam center of 300 μJy per epoch. Ten transient sources were detected with a significance threshold such that only one false positive would be expected. Of these transients, eight were detected in only a single epoch. Two transients were too faint to be detected in individual epochs but were detected in 2 month averages. None of the 10 transients was detected in longer term averages or associated with persistent emission in the deep image produced from the combination of all epochs. The cumulative rate for the short-timescale radio transients above 370 μJy at 5 and 8.4 GHz is 0.07 deg-2 yr -1 ≲ R ≲ 40 deg-2 yr-1, where the uncertainty is due to the unknown duration of the transients, 20 minutes < tchar < 7 days. A two-epoch survey for transients will detect 1.5 ± 0.4 transients per square degree above a flux density of 3 70 μJy. Two transients are associated with galaxies at z = 0.040 and z = 0.249. These may be similar to the peculiar Type Ib/c radio supernova SN 1998bw associated with GRB 980428. We detect no counterparts for six transients in deep optical and infrared imaging. The hosts and progenitors of these transients are unknown. © 2007. The American Astronomical Society. All rights reserved.

In a 1967 patent, D. M. Scruggs found that the room temperature ductility of molybdenum is improved by adding several volume percent of MgAl2O4 spinel particles. The present work substantiates Scruggs' claim – with increasing MgAl2O4 volume fraction the ductility of Mo–MgAl2O4 is found to pass through a maximum near 2.5 vol%. Scruggs postulated that gettering of detrimental impurities was responsible for this effect. In the present work, fracture initiated at microcracks that formed on the Mo–MgAl2O4 specimen surfaces during tensile testing. The ductility maximum is interpreted in terms of the change in the microcrack size (which is assumed to scale with the grain size) and the ultimate tensile stress, as the MgAl2O4 volume fraction increases. Fracture occurs once a critical local stress-intensity factor, which is approximately independent of the MgAl2O4 volume fraction, is reached.

The association of Type Ic SNe with long-duration GRBs is well established. We endeavor, through accurate ground-based observational campaigns, to characterize these SNe at increasingly high redshifts. We obtained a series of optical photometric and spectroscopic observations of the Type Ic SN2012bz associated with the Swift long-duration GRB120422A (z=0.283) using the 3.6-m TNG and the 8.2-m VLT telescopes. The peak times of the light curves of SN2012bz in various optical filters differ, with the B-band and i'-band light curves reaching maximum at ~9 and ~23 rest-frame days, respectively. The bolometric light curve has been derived from individual bands photometric measurements, but no correction for the unknown contribution in the near-infrared (probably around 10-15%) has been applied. Therefore, the present light curve should be considered as a lower limit to the actual UV-optical-IR bolometric light curve. This pseudo-bolometric curve reaches its maximum (Mbol = -18.56 +/- 0.06) at 13 +/- 1 rest-frame days; it is similar in shape and luminosity to the bolometric light curves of the SNe associated with z<0.2 GRBs and more luminous than those of SNe associated with XRFs. A comparison with the model generated for the bolometric light curve of SN2003dh suggests that SN2012bz produced only about 15% less 56Ni than SN2003dh, about 0.35 Msol. Similarly the VLT spectra of SN2012bz, after correction for Galactic extinction and for the contribution of the host galaxy, suggest comparable explosion parameters with those observed in SN2003dh (EK~3.5 x 10^52 erg, Mej~7 Msol) and a similar progenitor mass (~25-40 Msol). GRB120422A is consistent with the Epeak-Eiso and the EX,iso-Egamma,iso-E_peak relations. GRB120422A/SN2012bz shows the GRB-SN connection at the highest redshift so far accurately monitored both photometrically and spectroscopically.

Boron-containing molybdenum silicides have been the focus of significant research of late due to their potentially superior low-temperature.

State machine replication protocols, like MultiPaxos and Raft, are a critical component of many distributed systems and databases. However, these protocols offer relatively low throughput due to several bottlenecked components. Numerous existing protocols fix different bottlenecks in isolation but fall short of a complete solution. When you fix one bottleneck, another arises. In this paper, we introduce compartmentalization, the first comprehensive technique to eliminate state machine replication bottlenecks. Compartmentalization involves decoupling individual bottlenecks into distinct components and scaling these components independently. Compartmentalization has two key strengths. First, compartmentalization leads to strong performance. In this paper, we demonstrate how to compartmentalize MultiPaxos to increase its throughput by 6x on a write-only workload and 16x on a mixed read-write workload. Unlike other approaches, we achieve this performance without the need for specialized hardware. Second, compartmentalization is a technique, not a protocol. Industry practitioners can apply compartmentalization to their protocols incrementally without having to adopt a completely new protocol.

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 Artificial metalloenzymes (ArMs), created by introducing synthetic cofactors into protein scaffolds, are an emerging class of catalyst for non‐natural reactions. Although many classes of ArMs are known, in vitro reconstitution of cofactors and proteins has been a limiting step in the high‐throughput screening and directed evolution of ArMs because purification of individual host proteins is time‐consuming. We describe the application of a platform to combine mutants of the P450 enzyme CYP119 and the cofactor Ir(Me)MPIX in vivo , by coexpression of the CYP119 mutants with the heme transporter encoded by the hug operon, to the directed evolution of ArMs containing Ir(Me)MPIX in whole cells. We applied this platform to the development an ArMs catalyzing the insertion of the acyclic carbene from α‐diazopropanoate esters (Me‐EDA) into the N−H bonds of N‐alkyl anilines, a combination of carbene and amine classes for which mutant enzymes of natural hemoproteins previously reacted with low enantioselectivity. The mutants of the artificial metalloenzyme Ir(Me)CYP119 identified by an evolution campaign involving more than 4000 mutants are shown to catalyze the reaction of Me‐EDA with N‐methyl anilines to form chiral chiral amino esters with high TON and good enantioselectivity, thereby demonstrating that the directed evolution of ArMs can rival that of natural enzymes in vivo .