Growth Mechanism and Electronic Structure of Zn_3P_2 on the Ga-Rich GaAs(001) Surface

The growth of epitaxial Zn_3P_2 films on III–V substrates unlocks a promising pathway toward high-efficiency, earth-abundant photovoltaic devices fabricated on reusable, single-crystal templates. The detailed chemical, structural, and electronic properties of the surface and interface of pseudomorphic Zn_3P_2 epilayers grown on GaAs(001) were investigated using scanning tunneling microscopy/spectroscopy and high-resolution X-ray photoelectron spectroscopy. Two interesting features of the growth process were observed: (1) vapor-phase P4 first reacts with the Ga-rich GaAs surface to form an interfacial GaP layer with a thickness of several monolayers, and (2) a P-rich amorphous overlayer is present during the entire film growth process, beneath which a highly ordered Zn_3P_2 crystalline phase is precipitated. These features were corroborated by transmission electron micrographs of the Zn_3P_2/GaAs interface as well as density functional theory calculations of P reactions with the GaAs surface. Finally, the valence-band offset between the crystalline Zn_3P_2 epilayer and the GaAs substrate was determined to be ΔE_V = 1.0 ± 0.1 eV, indicating the formation of a hole-depletion layer at the substrate surface which may inhibit formation of an ohmic contact

ADAM10 mediates the house dust mite-induced release of chemokine ligand CCL20 by airway epithelium

Background: House dust mite (HDM) acts on the airway epithelium to induce airway inflammation in asthma. We previously showed that the ability of HDM to induce allergic sensitization in mice is related to airway epithelial CCL20 secretion. Objective: As a disintegrin and metalloprotease (ADAM)s have been implicated in chemokine shedding, we sought to determine their involvement in HDM-induced release of chemokines, including CCL20, by airway epithelial cells. Methods: We studied the effects of pharmacological ADAM inhibitors as well as ADAM10 and ADAM17 siRNA downregulation on chemokine release using (multiplex) ELISA in supernatants from HDM-exposed human bronchial epithelial 16HBE cells and primary normal human bronchial epithelial cells (NHBE) at 4-24 h. Results: House dust) mite markedly increased CCL20 levels in both 16HBE and NHBE cells (16-24 h). In 16HBE cells, the HDM-induced increase was observed as early as 4 h upon exposure and the use of specific inhibitors indicated the involvement of ADAM10/17-mediated shedding. siRNA knockdown of ADAM 10, but not of ADAM 17, significantly reduced the HDM-induced release of CCL20 in both 16HBE and NHBE cells. A similar effect was observed for HDM-induced CCL2, CCL5, and CXCL8 release in NHBE cells. The HDM-induced increase in CCL20 levels was not affected by protein synthesis inhibitor cycloheximide nor protein transport inhibitor monensin, indicating that HDM induces surface shedding of chemokines. Conclusion: Our data show for the first time that ADAM10 activity contributes to HDM-induced shedding of chemokines, including CCL20. The ADAM10/CCL20 axis may be a target for novel therapeutic strategies in asthma

Structural Evolution of MOF-Derived RuCo, A General Catalyst for the Guerbet Reaction

Guerbet alcohols, a class of β-branched terminal alcohols, find widespread application because of their low melting points and excellent fluidity. Because of the limitations in the activity and selectivity of existing Guerbet catalysts, Guerbet alcohols are not currently produced via the Guerbet reaction but via hydroformylation of oil-derived alkenes followed by aldol condensation. In pursuit of a one-step synthesis of Guerbet alcohols from simple linear alcohol precursors, we show that MOF-derived RuCo alloys achieve over a million turnovers in the Guerbet reaction of 1-propanol, 1-butanol, and 1-pentanol. The active catalyst is formed in situ from ruthenium-impregnated metal–organic framework MFU-1. XPS and XAS studies indicate that the precatalyst is composed of Ru precursor trapped inside the MOF pores with no change in the oxidation state or coordination environment of Ru upon MOF incorporation. The significantly higher reactivity of Ru-impregnated MOF versus a physical mixture of Ru precursor and MOF suggests that the MOF plays an important role in templating the formation of the active catalyst and/or its stabilization. XPS reveals partial reduction of both ruthenium and MOF-derived cobalt under the Guerbet reaction conditions, and TEM/EDX imaging shows that Ru is decorated on the edges of dense nanoparticles, as well as thin nanoplates of CoOx. The use of ethanol rather than higher alcohols as a substrate results in lower turnover frequencies, and RuCo recovered from ethanol upgrading lacks nanostructures with plate-like morphology and does not exhibit Ru-enrichment on the surface and edge sites. Notably, 1H and 31P NMR studies show that through use of K3PO4 as a base promoter in the RuCo-catalyzed alcohol upgrading, the formation of carboxylate salts, a common side product in the Guerbet reaction, was effectively eliminated

Imaging atomic-scale chemistry from fused multi-modal electron microscopy

Efforts to map atomic-scale chemistry at low doses with minimal noise using electron microscopes are fundamentally limited by inelastic interactions. Here, fused multi-modal electron microscopy offers high signal-to-noise ratio (SNR) recovery of material chemistry at nano- and atomic-resolution by coupling correlated information encoded within both elastic scattering (high-angle annular dark-field (HAADF)) and inelastic spectroscopic signals (electron energy loss (EELS) or energy-dispersive x-ray (EDX)). By linking these simultaneously acquired signals, or modalities, the chemical distribution within nanomaterials can be imaged at significantly lower doses with existing detector hardware. In many cases, the dose requirements can be reduced by over one order of magnitude. This high SNR recovery of chemistry is tested against simulated and experimental atomic resolution data of heterogeneous nanomaterials