Publications

Refractory high-entropy alloys (RHEAs) are designed for high elevated-temperature strength, with both edge and screw dislocations playing an important role for plastic deformation. However, they can also display a significant energetic driving force for chemical short-range ordering (SRO). Here, we investigate mechanisms underlying the mobilities of screw and edge dislocations in the body-centered cubic MoNbTaW RHEA over a wide temperature range using extensive molecular dynamics simulations based on a highly-accurate machine-learning interatomic potential. Further, we specifically evaluate how these mechanisms are affected by the presence of SRO. The mobility of edge dislocations is found to be enhanced by the presence of SRO, whereas the rate of double-kink nucleation in the motion of screw dislocations is reduced, although this influence of SRO appears to be attenuated at increasing temperature. Independent of the presence of SRO, a cross-slip locking mechanism is observed for the motion of screws, which provides for extra strengthening for refractory high-entropy alloy system.

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.

Photoelectrochemical (PEC) CO 2 reduction (PEC CO 2 R) is a prospective approach for utilizing solar energy to synthesize a variety of carbon-containing chemicals and fuels, the most valuable of which are multicarbon (C 2+ ) products, such as ethylene and ethanol. While these products can be produced with high faradaic efficiency using Cu, this occurs over a relatively narrow potential range, which, in turn, imposes constraints on the design of a device for PEC CO 2 R. Herein, we used continuum-scale modeling to simulate the solar-to-C 2+ (STC 2+ ) efficiency of PEC CO 2 R devices fed with CO 2 -saturated, 0.1 M CsHCO 3 . We then explored how cell architecture and the use of single or dual photoelectrode(s) alters the optimal combination of photoelectrode bandgaps for high STC 2+ efficiency. Ultimately, this work provides guidance for the co-design of the device architecture and photoelectrode bandgaps required to achieve high STC 2+ efficiency. The insights gained are then used to identify systems that yield the highest amount of C 2+ products throughout the day and year.

Heterogeneous rhodium catalysts supported on SiO2 were modified with PPh3 for the gas-phase hydroformylation of propene to produce n- and isobutanal. High selectivity to aldehydes was achieved, with no propane or alcohols formed. Investigation of the effects of reaction temperature, reactant partial pressures, total pressure, and PPh3/Rh ratio suggested that the supported catalyst behaved similarly to the homogeneous catalyst. In particular, the supported catalyst showed similar activation energies and partial and total pressure dependences of the reaction rates to those observed in homogeneous, liquid-phase reactions. The first order dependence of the hydroformylation rate on the partial pressures of propene, CO, and H2 individually led to a cubic dependence of butanal formation on total pressure for equimolar reactant mixtures. High regioselectivity with a typical n/i ratio of 14 was achieved.

Abstract Three new post‐synthetic modification reactions, namely amidation, esterification, and thioesterification, were demonstrated on a novel highly crystalline two‐dimensional covalent organic framework (COF), COF‐616, bearing pre‐installed carboxyl groups. The strategy can be used to introduce a large variety of functional groups into COFs and the modifications can be carried out under mild reaction conditions, with high yields, and an easy work‐up protocol. As a proof of concept, various chelating functionalities were successfully incorporated into COF‐616 to yield a family of adsorbents for efficient removal of several contaminants in the water.

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.

We measured the contribution of glucose to hepatic cytosolic acetyl-CoA in vivo in rats and compared it with the phosphorylation state of a potentially regulatory enzyme complex [pyruvate dehydrogenase (PDH)]. Xenobiotic probes were used to sample hepatic cytosolic acetyl-CoA [acetylated sulfamethoxazole (SMX)] and UDP-glucose (glucuronidated acetaminophen) in vivo during [U-14C]glucose infusions. Percent active (dephosphorylated) form of PDH (PDHa) was determined on freeze-clamped liver. First, we confirmed using liver cell elutriation that acetylation of SMX occurs in parenchymal hepatocytes. Next, the fraction of cytosolic acetyl-CoA derived from [14C]glucose in vivo was shown to depend on dietary state. Specific activity of acetyl-CoA relative to plasma glucose or hepatic UDP-glucose was lower after 48 h fasting than after overnight fasting, and glucose refeeding (25 mg.kg-1.min-1 iv) maximally increased [14C]-glucose fractional contribution to acetyl-CoA within 2 h in the overnight-fasted but not in the prolonged fasted group. Hepatic PDHa demonstrated a similar but not identical pattern. The isotopic and enzymatic parameters showed significant correlations (r2 = 0.61 in 48-h fasted-refed group, r2 = 0.28 in overnight-fasted refed group), although [14C]glucose contribution to acetyl-CoA increased disproportionately compared with PDHa as refeeding progressed. The indirect pathway of UDP-glucose synthesis correlated inversely with the fractional contribution of glucose to acetyl-CoA. In summary, the fraction of hepatic acetyl-CoA derived from glucose in vivo is influenced by acute and chronic dietary factors and is only partially explained by PDHa. Regulation of the carbon source of hepatic acetyl-CoA in vivo and interactions suggested by these results (e.g., glucose-fatty acid cycle; branch-point regulation of glucose recycling) can be addressed in a quantitative fashion using this experimental framework.

We report the discovery by the Swift hard X-ray monitor of the transient source Swift J2058.4+0516 (Sw J2058+05). Our multi-wavelength follow-up campaign uncovered a long-lived (duration approximately greater than months), luminous X-ray (L(sub x.iso) approximates 3 X 10(exp47) erg/s) and radio (vL(sub v.iso) approximates 10(exp 42) erg/s) counterpart. The associated optical emission, however, from which we measure a redshift of 1.1853, is relatively faint, and this is not due to a large amount of dust extinction in the host galaxy. Based on numerous similarities with the recently discovered GRB 110328A / Swift 1164449.3+573451 (Sw 11644+57), we suggest that Sw J2058+05 may be the second member of a new class of relativistic outbursts resulting from the tidal disruption of a star by a supermassive black hole. If so, the relative rarity of these sources implies that either these outflows are extremely narrowly collimated (theta < 1 deg), or only a small fraction of tidal disruptions generate relativistic ejecta. Analogous to the case of long duration gamma-ray bursts and core-collapse supernovae, we speculate that the spin of the black hole may be a necessary condition to generate the relativistic component. Alternatively, if powered by gas accretion (i.e., an active galactic nucleus), this would imply that some galaxies can transition from apparent quiescence to a radiatively efficient state of accretion on quite short time scales.

Abstract The aryldiazonium cations as source of electrophilic nitrogen are used for the first time in an asymmetric reaction.