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Identifying Waste Burning Plumes Using High-Resolution Satellite Imagery and Machine Learning: A Case Study in the Maldives
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Uranium Chemistry: Identifying the Next Frontiers
While uranium is the most extensively studied actinide in terms of chemical properties, there remains much to be explored about its fundamental chemistry. Organometallic and organoactinide chemistry first emerged in the 1950s with research that found inspiration from transition-metal chemistry with the synthesis and characterization of uranocene, expanding new opportunities for organoactinide chemistry. Since then, a significant amount of research has pursued many avenues characterizing the fundamental nature of the f orbitals and their modes of bonding as well as their potential in catalysis. Uranium(III/IV) arene complexes dominate much of uranium organometallic chemistry, with bonding interactions stabilized by δ-back-bonding. Recent additions to this area of chemistry include the first UI and new additions of U II organouranium compounds. Uranium–transition metal complexes are still rare and maintain U IV oxidation states, with variable bond lengths determining the transition-metal oxidation state. Resultant reactivities are discussed as synthetic complexes, and unique bonding and coordination motifs are highlighted. In conclusion, this Viewpoint will focus on significant developments in uranium chemistry from the last 15 years while considering key areas for future research.
Linear Free Energy Relationships Associated with Hydride Transfer From [(6,6'-R 2 -bpy)Re(CO) 3 H]: A Cautionary Tale in Identifying Hydrogen Bonding Effects in the Secondary Coordination Sphere
Here, six rhenium hydride complexes, [(6,6'-R 2 -bpy)Re(CO) 3 H] (bpy = 2,2'-bipyridine, R = OEt, OMe, NHMe, Me, F, Br), were synthesized. These complexes insert CO 2 to form rhenium formate complexes of the type [(6,6'-R 2 -bpy)Re(CO) 3 {OC(O)H}]. All the rhenium formate species were characterized using X-ray crystallography, which revealed that the bpy ligand is not coplanar with the metal coordination plane containing the two nitrogen donors of the bpy ligand but tilted. A solid-state structure of [(6,6'-Me 2 -bpy)Re(CO) 3 H] determined using MicroED also featured a tilted bpy ligand. The kinetics of CO 2 insertion into complexes of the type [(6,6'-R 2 -bpy)Re(CO) 3 H] were measured experimentally and the thermodynamic hydricities of [(6,6'-R 2 -bpy)Re(CO) 3 H] species were determined using theoretical calculations. A Brønsted plot constructed using the experimentally determined rate constants for CO 2 insertion and the calculated thermodynamic hydricities for [(6,6'-R 2 -bpy)Re(CO) 3 H] revealed a linear free energy relationship (LFER) between thermodynamic and kinetic hydricity. This LFER is different to the previously determined relationship for CO 2 insertion into complexes of the type [(4,4'-R 2 -bpy)Re(CO) 3 H]. At a given thermodynamic hydricity, CO 2 insertion is faster for complexes containing a 6,6'-substituted bpy ligand. This is likely in part due to the tilting observed for systems with 6,6'-substituted bpy ligands. Notably, the 6,6'-(NHMe) 2 -bpy ligand could in principle stabilize the transition state for CO 2 insertion via hydrogen bonding. This work shows that if only the rate of CO 2 insertion into [(6,6'-(NHMe) 2 -bpy)Re(CO) 3 H] is compared to [(4,4'-R 2 -bpy)Re(CO) 3 H] systems, the increase in rate could be easily attributed to hydrogen bonding, but in fact all 6,6'-substituted systems lead to faster than expected rates.
Cation-poor complex metallic alloys in Ba(Eu)–Au–Al(Ga) systems: Identifying the keys that control structural arrangements and atom distributions at the atomic level
Four complex intermetallic compounds BaAu 6±x Ga 6±y (x = 1, y = 0.9) (I), BaAu 6±x Al 6±y (x = 0.9, y = 0.6) (II), EuAu 6.2 Ga 5.8 (III), and EuAu 6.1 Al 5.9 (IV) have been synthesized, and their structures and homogeneity ranges have been determined by single crystal and powder X-ray diffraction. Whereas I and II originate from the NaZn 13 -type structure (cF104–112, Fm3C), III (tP52, P4/nbm) is derived from the tetragonal Ce 2 Ni 17 Si 9 -type, and IV (oP104, Pbcm) crystallizes in a new orthorhombic structure type. Both I and II feature formally anionic networks with completely mixed site occupation by Au and triel (Tr = Al, Ga) atoms, while a successive decrease of local symmetry from the parental structures of I and II to III and, ultimately, to IV correlates with increasing separation of Au and Tr on individual crystallographic sites. Density functional theory-based calculations were employed to determine the crystallographic site preferences of Au and the respective triel element to elucidate reasons for the atom distribution (“coloring scheme”). Chemical bonding analyses for two different “EuAu 6 Tr 6 ” models reveal maximization of the number of heteroatomic Au–Tr bonds as the driving force for atom organization. The Fermi levels fall in broad pseudogaps for both models allowing some electronic flexibility. Spin-polarized band structure calculations on the “EuAu 6 Tr 6 ” models hint to singlet ground states for europium and long-range magnetic coupling for both EuAu 6.2 Ga 5.8 (III) and EuAu 6.1 Al 5.9 (IV). This is substantiated by experimental evidence because both compounds show nearly identical magnetic behavior with ferromagnetic transitions at T C = 6 K and net magnetic moments of 7.35 μB/f.u. at 2 K. As a result, the effective moments of 8.3 μB/f.u., determined from Curie–Weiss fits, point to divalent oxidation states for europium in both III and IV.
Clustering Protein Binding Pockets and Identifying Potential Drug Interactions: A Novel Ligand-Based Featurization Method
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Hinge Binder Scaffold Hopping Identifies Potent Calcium/Calmodulin-Dependent Protein Kinase Kinase 2
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Potent Antimalarials with Development Potential Identified by Structure-Guided Computational Optimiz
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Leveraging Structure-Based Drug Design to Identify Next-Generation MAT2A Inhibitors, Including Brain
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Acetyl-Click Screening Platform Identifies Small-Molecule Inhibitors of Histone Acetyltransferase 1 (HAT1)
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Application of Structure-Based Design and Parallel Chemistry to Identify a Potent, Selective, and Brain Penetrant Phosphodiesterase 2A Inhibitor
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To Boldly Look Where No One Has Looked Before: Identifying the Primary Photoproducts of Acetylacetone
We investigate the gas-phase photochemistry of the enolone tautomer of acetylacetone (pentane-2,4-dione) following S2(ππ*) ← S o excitation at λ = 266 and 248 nm, using three complementary time-resolved spectroscopic methods. Contrary to earlier reports, which claimed to study 1-photon excitation of acetylacetone and found OH and CH 3 as the only important gas-phase products, we detect fifteen unique primary photoproducts and demonstrate that five of them, including OH and CH 3 , arise solely by multiphoton excitation. We assign the 1-photon products to six photochemical channels and show that the most significant pathway is tautomerization to the diketone form, which is likely an intermediate in several of the other product channels. Furthermore, we measure the equilibrium constant of this keto-enol tautomerization on S0 from 320 to 600 K and extract ΔH = 4.1 ± 0.3 kcal∙mol –1 , and ΔS = 6.8 ± 0.5 cal∙mol –1 ∙K –1 using a van’t Hoff analysis. We correct the C–OH bond dissociation energy in acetylacetone, previously determined as 90 kcal∙mol –1 by theory and experiment, to a new value of 121.7 kcal∙mol –1 . Here, our experiments and electronic structure calculations provide evidence that some of the product channels, including phototautomerization, occur on S o , while others likely occur on excited triplet surfaces. Although the strong oscillator strength of the S 2 ← S o transition results from the (ππ*) excitation of the C=C–C=O backbone, similar to conjugated polyenes, the participation of triplets in the dissociation pathways of acetylacetone appears to have more in common with ketone photochemistry.
Hotspot Coevolution Is a Key Identifier of Near-Native Protein Complexes
Protein–protein interactions play a key role in mediating numerous biological functions, with more than half the proteins in living organisms existing as either homo- or hetero-oligomeric assemblies. Protein subunits that form oligomers minimize the free energy of the complex, but exhaustive computational search-based docking methods have not comprehensively addressed the challenge of distinguishing a natively bound complex from non-native forms. Current protein docking approaches address this problem by sampling multiple binding modes in proteins and scoring each mode, with the lowest-energy (or highest scoring) binding mode being regarded as a near-native complex. However, high-scoring modes often match poorly with the true bound form, suggesting a need for improvement of the scoring function. Here in this study, we propose a scoring function, KFC-E, that accounts for both conservation and coevolution of putative binding hotspot residues at protein–protein interfaces. We tested KFC-E on four benchmark sets of unbound examples and two benchmark sets of bound examples, with the results demonstrating a clear improvement over scores that examine conservation and coevolution across the entire interface.
LaMnO 3 Dopants for Efficient Thermochemical Water Splitting Identified by Density Functional Theory Calculations
While ceria is the standard material for two-step water splitting, perovskites are emerging as viable alternatives. In this work, based on the orthorhombic LaMnO 3 supercell, we substitute Li Na K Rb Mg Ca Sr Ba on the A-sites (La sites) and Al Ga In Mg Zn on the B-sites (Mn sites) at a concentration of 37.5%. The range of temperature and oxygen partial pressure at which each composition is stable is predicted. For compositions that are stable in relevant temperature and pressure ranges, the oxygen vacancy formation energies are determined for all of the oxygen vacancy site positions available in the computational supercell. Mg, Ca, Sr, and Ba A-site-substituted LaMnO 3 and Al and In B-site-substituted LaMnO 3 meet these two criteria for candidates in solar-thermal water splitting applications. Finally, oxygen vacancy formation energy can also be controlled by adjusting the doping strategy.