Ethylene oxidation by Ag catalysts has been extensively investigated over the past few decades, but many key fundamental issues about this important catalytic system are still unresolved. This overview of the selective oxidation of ethylene to ethylene oxide by Ag catalysts critically examines the experimental and theoretical literature of this complex catalytic system: (i) the surface chemistry of silver catalysts (single crystal, powder/foil, and supported Ag/α-Al2O3), (ii) the role of promoters, (iii) the reaction kinetics, (iv) the reaction mechanism, (v) density functional theory (DFT), and (vi) microkinetic modeling. Only in the past few years have the modern catalysis research tools of in situ/operando spectroscopy and DFT calculations been applied to begin establishing fundamental structure−activity/selectivity relationships. This overview of the ethylene oxidation reaction by Ag catalysts covers what is known and what issues still need to be determined to advance the rational design of this important catalytic system.
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Modulation of plant growth and development through altered ethylene binding affinity of the ethylene receptor ETR1
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Abstract The phytohormone ethylene controls plant growth and stress responses. Ethylene-exposed dark-grown Arabidopsis seedlings exhibit dramatic growth reduction, yet the seedlings rapidly return to the basal growth rate when ethylene gas is removed. However, the underlying mechanism governing this acclimation of dark-grown seedlings to ethylene remains enigmatic. Here, we report that ethylene triggers the translocation of the Raf-like protein kinase CONSTITUTIVE TRIPLE RESPONSE1 (CTR1), a negative regulator of ethylene signaling, from the endoplasmic reticulum to the nucleus. Nuclear-localized CTR1 stabilizes the ETHYLENE-INSENSITIVE3 (EIN3) transcription factor by interacting with and inhibiting EIN3-BINDING F-box (EBF) proteins, thus enhancing the ethylene response and delaying growth recovery. Furthermore, Arabidopsis plants with enhanced nuclear-localized CTR1 exhibited improved tolerance to drought and salinity stress. These findings uncover a mechanism of the ethylene signaling pathway that links the spatiotemporal dynamics of cellular signaling components to physiological responses.more » « less
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The gaseous hormone ethylene is perceived in plants by membrane-bound receptors, the best studied of these being ETR1 from Arabidopsis. Ethylene receptors can mediate a response to ethylene concentrations at less than one part per billion; however, the mechanistic basis for such high-affinity ligand binding has remained elusive. Here we identify an Asp residue within the ETR1 transmembrane domain that plays a critical role in ethylene binding. Site-directed mutation of the Asp to Asn results in a functional receptor that has a reduced affinity for ethylene, but still mediates ethylene responses in planta. The Asp residue is highly conserved among ethylene receptor-like proteins in plants and bacteria, but Asn variants exist, pointing to the physiological relevance of modulating ethylene-binding kinetics. Our results also support a bifunctional role for the Asp residue in forming a polar bridge to a conserved Lys residue in the receptor to mediate changes in signaling output. We propose a new structural model for the mechanism of ethylene binding and signal transduction, one with similarities to that found in a mammalian olfactory receptor.more » « less
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