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The large ribosomal subunit has several important structures essential to translation. These include the peptidyl transferase center (PTC) - which is the site where the peptide bond is formed - and a large, internal, water-filled tube through which the nascent polypeptide moves. This latter structure is called the Peptide Exit Tunnel, and it begins at the PTC and spans the body of the large ribosomal subunit. During translation, as the nascent polypeptide chain is synthesized, it passes through...
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Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
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The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
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Ce=O Terminated CeO2.

David C Grinter1,2, Michael Allan1, Hyun Jin Yang1

  • 1Department of Chemistry and London Centre for Nanotechnology, University College London, 20 Gordon Street, London, WC1H 0AJ, UK.

Angewandte Chemie (International Ed. in English)
|April 7, 2021
PubMed
Summary
This summary is machine-generated.

Researchers observed a rare double-bonded oxygen on cerium oxide surfaces, crucial for understanding cerium oxide

Keywords:
cerium dioxidedensity functional calculationsheterogeneous catalysismultiple bondsscanning tunnelling microscopy

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Area of Science:

  • Surface Science
  • Materials Chemistry
  • Catalysis

Background:

  • Multiply bonded lanthanide oxo groups are uncommon in coordination chemistry.
  • A surface termination involving such bonds on lanthanide oxides has not been previously documented.

Purpose of the Study:

  • To report the first observation of a multiply bonded oxo group on a lanthanide oxide surface.
  • To investigate the structural and electronic properties of this novel surface termination.
  • To explore the implications for ceria's catalytic activity.

Main Methods:

  • Preparation of ≈3 nm thick ceria islands on a Platinum(111) surface.
  • Characterization using scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), and high-resolution electron energy loss spectroscopy (HREELS).
  • Validation through density functional theory (DFT) calculations.

Main Results:

  • Observation of a cerium-oxygen double bond (Ce=O) on a ceria (CeO2) surface reconstruction.
  • Experimental Ce=O stretching frequency of 775 cm-1, consistent with DFT calculations (766 cm-1).
  • DFT predicts a weak Ce=O bond and a low oxygen vacancy formation energy (0.85 eV).

Conclusions:

  • The identified Ce=O surface termination is a rare phenomenon in lanthanide coordination chemistry.
  • The weak Ce=O bond facilitates oxygen removal and CeIV to CeIII reduction.
  • This finding is significant for understanding the catalytic properties of ceria-based materials.