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Affiliation involving Company Points of views on Ethnic background and also National Healthcare Differences with Patient Views of Care and also Wellness Outcomes.
The need to characterize and track coastal hypoxia has led to the development of geostatistical models based on in situ observations of dissolved oxygen (DO) and mechanistic models based on a representation of biophysical processes. To integrate the benefits of these two distinct modeling approaches, we develop a space-time geostatistical framework for synthesizing DO observations with hydrodynamic-biogeochemical model simulations and meteorological time series (as covariates). This fusion-based approach is used to estimate hypoxia in the northern Gulf of Mexico across summers from 1985 to 2017. Deterministic trends with dynamic covariates explain over 35% of the variability in DO. Moreover, cross-validation results indicate that 58% of DO variability is explained when combining these trends with spatiotemporal interpolation, which is substantially better than mechanistic or conventional geostatistical hypoxia modeling alone. The fusion-based approach also reduces hypoxic area uncertainties by 11% on average and up to 40% in months with sparse sampling. Moreover, our new estimates of mean summer hypoxic area changed by >10% in a majority of years, relative to previous geostatistical estimates. These fusion-based estimates can be a valuable resource when assessing the influence of hypoxia on the coastal ecosystem.The potential applications of metal-organic cages (MOCs) are mostly achieved through specific host-guest interactions within their cavities. Electronic applications would require an effective electron transport pathway, which has been extensively studied in hybrid organic-inorganic materials with extended structures. These properties have not been considered for MOCs because cage-to-cage interactions in these materials have rarely been examined and are challenging to functionalize. We report here a previously unobserved actinide-based MOC assembled from four hexagonal-bipyramidal-coordinated uranyl ions and six bidentate flexible ligands. ALLN Remarkably, each isolated cage is further interlocked with six adjacent ones through mechanical bonds, resulting in the first case of a 0D → 3D f-element polycatenated metal-organic cage, SCU-14. Long-range π-π stacking extending throughout the structure is built via polycatenation, providing a visible carrier transmission path. SCU-14 is also an extremely rare case of an intrinsically semiconductive MOC with a wide band gap of 2.61 eV. Combined with the high X-ray attenuation efficiency, SCU-14 can effectively convert X-ray photons to electrical current signals and presents a promising sensitivity of 54.93 μC Gy-1 cm-2.A single crystal of the boron subhydride B104.67(4)H3 was serendipitously obtained while attempting to synthesize β-boron. An accurate crystal structure analysis revealed a distorted β-boron framework with the noncentrosymmetric space group R3m. We have found one interstitial site occupied by boron. The site related by inversion remains empty. The distortions of the framework result in ideal environments for the interstitial boron atom, and for the three hydrogen atoms at bridging positions between icosahedral B12 groups, they result in ideal B-H distances of 1.33 Å. B104.67(4)H3 is a borane with the lowest amount of hydrogen recorded to date, and it is the first compound with a noncentrosymmetrically distorted β-boron framework.The purpose of this Viewpoint is to provide a broad-ranging update of advances in the coordination chemistry of redox-active (noninnocent) 2-aminophenolates, with emphasis on two ligand backbone structural parameters, the average of C-O and C-N (C-O/N) bond distances and Δa values, signifying the degree of bond-length alternation in the six-membered ring, in order to identify the redox level of the coordinated ligands. In the absence of magnetic, spectroscopic, and redox results, it has been established that it is possible to assign the electronic ground state of a coordination complex of 2-aminophenolates with consideration of charge, metal-ligand bond distances, and two very promising ligand backbone structural parameters. From a closer look at the sensitive ligand backbone metrical parameters of a diversified group of about 120 transition-metal complexes, a few very useful generalizations have been made.For the first time, fully characterized and stable trinuclear "double sandwich" molecules are reported with Hg(II) ion using a highly flexible porphyrin dimer. The molecules display interesting and intense luminescence properties at room temperature. The present investigation clearly demonstrates that attractive mercurophilic interactions do play an essential role in bringing two porphyrin macrocycles exactly on top of each other with an unfavorable fully eclipsed geometry to produce short Hg···Hg distances. Interactions between Hg(II) dz2 orbitals provide the directionality with a linear Hg3 core having short Hg···Hg distances despite the fact that ligand framework is highly flexible.Understanding the evolution of the structure and properties in metals from molecule-like to bulk-like has been a long sought fundamental question in science, since Faraday's 1857 work. We report the discovery of a Janus nanomolecule, Au191(SPh-tBu)66 having both molecular and metallic characteristics, explored crystallographically and optically and modeled theoretically. Au191 has an anisotropic, singly twinned structure with an Au155 core protected by a ligand shell made of 24 monomeric [-S-Au-S-] and 6 dimeric [-S-Au-S-Au-S-] staples. The Au155 core is composed of an 89-atom inner core and 66 surface atoms, arranged as [Au3@Au23@Au63]@Au66 concentric shells of atoms. The inner core has a monotwinned/stacking-faulted face-centered-cubic (fcc) structure. Structural evolution in metal nanoparticles has been known to progress from multiply twinned, icosahedral, structures in smaller molecular sizes to untwinned bulk-like fcc monocrystalline nanostructures in larger nanoparticles. The monotwinned inner core structure of the ligand capped Au191 nanomolecule provides the critical missing link, and bridges the size-evolution gap between the molecular multiple-twinning regime and the bulk-metal-like particles with untwinned fcc structure. The Janus nature of the nanoparticle is demonstrated by its optical and electronic properties, with metal-like electron-phonon relaxation and molecule-like long-lived excited states. First-principles theoretical explorations of the electronic structure uncovered electronic stabilization through the opening of a shell-closing gap at the top of the occupied manifold of the delocalized electronic superatom spectrum of the inner core. The electronic stabilization together with the inner core geometric stability and the optimally stapled ligand-capping anchor and secure the stability of the entire nanomolecule.We report that an agile eight-membered cycloalkane can be stabilized by fusing a benzene ring on each side, substituted with proper functional groups. The conformational change of dibenzocycloocta-1,5-diene (DBCOD), a rigid-flexible-rigid organic moiety, from its Boat to Chair conformation requires an activation energy of 42 kJ/mol, which is substantially lower than those of existing submolecular shape-changing units. Experimental data corroborated by theoretical calculations demonstrate that intramolecular hydrogen bonding can stabilize Boat, whereas electron repulsive interaction from opposing ester substituents favors Chair. Intramolecular hydrogen bonding formed by 1,10-diamide substitution stabilizes Boat, spiking the temperature at which Boat and Chair can readily interchange from -60 to 60 °C. Concomitantly this intramolecular attraction raises the energy barrier from 42 kJ/mol for unsubstituted DBCOD to 68 kJ/mol for diamide-substituted DBCOD. Remarkably, this value falls within the range of the activation energy of highly efficient enzyme-catalyzed biological reactions. With shape changes once considered only possible with high energy, our work reveals a potential pathway exemplified by a specific submolecular structure to achieve low-energy-driven shape changes for the first time. The intrinsic cycle stability and high-energy output systems that would incur damage under high-energy stimuli could particularly benefit from this new kind of low-energy-driven shape-changing mechanism. This work has laid the basis to construct systems for low-energy-driven stimuli-responsive applications, hitherto a challenge to overcome.Single-layered, double-layered, and triple-layered Pt nanoparticles with a well-defined arrangement were encapsulated inside metal-organic frameworks (MOFs) to investigate the catalytic performance influenced by the progressive increasing of Pt nanoparticles inside MOFs; the results show that the catalytic activity of the Pt-MOF hybrid catalysts increases progressively with the progressive increasing of the Pt nanoparticles inside MOFs. Progressive increasing of Pt nanoparticles with a multiple-layered manner inside MOFs provides a new route for designing well-organized hybrid catalysts of noble metal nanoparticles and MOFs with enhanced catalytic activity.A two-ligand system composed of the predesigned multivalent and complementary terpyridine-based ligands was exploited to construct heteroleptic metallo-supramolecules and to investigate the self-assembly mechanism. Molecular stellation of the trimeric hexagon [Cd6L 2 3] gave rise to the exclusive self-assembly of the star hexagon [Cd18L 1 6L 3 3] through complementary ligand pairing between the ditopic and octatopic tectons. To understand how the intermolecular heteroleptic complexation influenced the self-assembly pathway, the star hexagon was truncated into two triangular fragments [Cd12L 1 3L 4 3] and [Cd12L 1 3L 5 3]. In the self-assembly of [Cd12L 1 3L 4 3], the conformational movements of hexatopic ligand L 4 could be regulated by L 1 to promote the subsequent coordination event, which was the key step to the successful multicomponent self-assembly. In contrast, the formation of [Cd12L 1 3L 5 3] was hampered by the geometrically mismatched intermediates.Perovskite structures of organic and inorganic halides are peculiar structures with many interesting properties. Using their photoelectric effect, the structures have been used in photocells, photoelectric sensors, and light-emitting diodes. In conventional perovskite film crystallization, which is a one-step method, the MAPbI3 crystals form disordered needlelike crystals at room temperature. Such needlelike crystal films have rough surfaces and low coverage to the substrate, resulting in insignificant photoelectric effects. With the assistance of an electric field and three-dimensional (3D) printing, the direction of the perovskite needlelike crystal can be arranged to make it orderly. In this way, the photoelectric sensor of the ordered MAPbI3 perovskite needlelike crystal film can be prepared. This sensor has high sensitivity, high stability, and high response speed. Moreover, it has anisotropy and higher photoelectric sensitivity in the direction perpendicular to the needle crystal. Most interestingly, the sensors respond differently to polarized light in different directions, and this effect can be used to detect the direction and degree of polarization of polarized light.
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