Oligonuclear Ferrocene Amides: Mixed-Valent Peptides and Potential Redox-Switchable Foldamers
- Publikationstyp:
- Zeitschriftenaufsatz
- Metadaten:
-
- Autoren
- Daniel Siebler
- Michael Linseis
- Teuta Gasi
- Luca M Carrella
- Rainer F Winter
- Christoph Foerster
- Katja Heinze
- Autoren-URL
- https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000290159000023&DestLinkType=FullRecord&DestApp=WOS_CPL
- DOI
- 10.1002/chem.201002101
- Externe Identifier
- Clarivate Analytics Document Solution ID: 758IY
- PubMed Identifier: 21274954
- ISSN
- 0947-6539
- Ausgabe der Veröffentlichung
- 16
- Zeitschrift
- CHEMISTRY-A EUROPEAN JOURNAL
- Schlüsselwörter
- foldamers
- iron
- metallocenes
- mixed-valent compounds
- peptides
- Paginierung
- 4540 - 4551
- Datum der Veröffentlichung
- 2011
- Status
- Published
- Titel
- Oligonuclear Ferrocene Amides: Mixed-Valent Peptides and Potential Redox-Switchable Foldamers
- Sub types
- Article
- Ausgabe der Zeitschrift
- 17
Datenquelle: Web of Science (Lite)
- Andere Metadatenquellen:
-
- Abstract
- <jats:title>Abstract</jats:title><jats:p>Trinuclear ferrocene tris‐amides were synthesized from an Fmoc‐ or Boc‐protected ferrocene amino acid, and hydrogen‐bonded zigzag conformations were determined by NMR spectroscopy, molecular modelling, and X‐ray diffraction. In these ordered secondary structures orientation of the individual amide dipole moments approximately in the same direction results in a macrodipole moment similar to that of α‐helices composed of α‐amino acids. Unlike ordinary α‐amino acids, the building blocks in these ferrocene amides with defined secondary structure can be sequentially oxidized to mono‐, di‐, and trications. Singly and doubly charged mixed‐valent cations were probed experimentally by Vis/NIR, paramagnetic <jats:sup>1</jats:sup>H NMR and Mössbauer spectroscopy and investigated theoretically by DFT calculations. According to the appearance of intervalence charge transfer (IVCT) bands in solution, the ferrocene/ferrocenium amides are described as Robin–Day class II mixed‐valent systems. Mössbauer spectroscopy indicates trapped valences in the solid state. The secondary structure of trinuclear ferrocene tris‐amides remains intact (coiled form) upon oxidation to mono‐ and dications according to DFT calculations, while oxidation to the trication should break the intramolecular hydrogen bonding and unfold the ferrocene peptide (uncoiled form).</jats:p>
- Autoren
- Daniel Siebler
- Michael Linseis
- Teuta Gasi
- Luca M Carrella
- Rainer F Winter
- Christoph Förster
- Katja Heinze
- DOI
- 10.1002/chem.201002101
- eISSN
- 1521-3765
- ISSN
- 0947-6539
- Ausgabe der Veröffentlichung
- 16
- Zeitschrift
- Chemistry – A European Journal
- Sprache
- en
- Online publication date
- 2011
- Paginierung
- 4540 - 4551
- Datum der Veröffentlichung
- 2011
- Status
- Published
- Herausgeber
- Wiley
- Herausgeber URL
- http://dx.doi.org/10.1002/chem.201002101
- Datum der Datenerfassung
- 2023
- Titel
- Oligonuclear Ferrocene Amides: Mixed‐Valent Peptides and Potential Redox‐Switchable Foldamers
- Ausgabe der Zeitschrift
- 17
Datenquelle: Crossref
- Abstract
- Trinuclear ferrocene tris-amides were synthesized from an Fmoc- or Boc-protected ferrocene amino acid, and hydrogen-bonded zigzag conformations were determined by NMR spectroscopy, molecular modelling, and X-ray diffraction. In these ordered secondary structures orientation of the individual amide dipole moments approximately in the same direction results in a macrodipole moment similar to that of α-helices composed of α-amino acids. Unlike ordinary α-amino acids, the building blocks in these ferrocene amides with defined secondary structure can be sequentially oxidized to mono-, di-, and trications. Singly and doubly charged mixed-valent cations were probed experimentally by Vis/NIR, paramagnetic ¹H NMR and Mössbauer spectroscopy and investigated theoretically by DFT calculations. According to the appearance of intervalence charge transfer (IVCT) bands in solution, the ferrocene/ferrocenium amides are described as Robin-Day class II mixed-valent systems. Mössbauer spectroscopy indicates trapped valences in the solid state. The secondary structure of trinuclear ferrocene tris-amides remains intact (coiled form) upon oxidation to mono- and dications according to DFT calculations, while oxidation to the trication should break the intramolecular hydrogen bonding and unfold the ferrocene peptide (uncoiled form).
- Addresses
- Institute of Inorganic Chemistry and Analytical Chemistry, Johannes Gutenberg-University of Mainz, Duesbergweg 10-14, 55128 Mainz, Germany.
- Autoren
- Daniel Siebler
- Michael Linseis
- Teuta Gasi
- Luca M Carrella
- Rainer F Winter
- Christoph Förster
- Katja Heinze
- DOI
- 10.1002/chem.201002101
- eISSN
- 1521-3765
- Externe Identifier
- PubMed Identifier: 21274954
- Open access
- false
- ISSN
- 0947-6539
- Ausgabe der Veröffentlichung
- 16
- Zeitschrift
- Chemistry (Weinheim an der Bergstrasse, Germany)
- Schlüsselwörter
- Ferrous Compounds
- Amides
- Peptides
- Magnetic Resonance Spectroscopy
- Molecular Structure
- Molecular Conformation
- Oxidation-Reduction
- Models, Molecular
- Metallocenes
- Sprache
- eng
- Medium
- Print-Electronic
- Online publication date
- 2011
- Paginierung
- 4540 - 4551
- Datum der Veröffentlichung
- 2011
- Status
- Published
- Datum der Datenerfassung
- 2011
- Titel
- Oligonuclear ferrocene amides: mixed-valent peptides and potential redox-switchable foldamers.
- Sub types
- Research Support, Non-U.S. Gov't
- Journal Article
- Ausgabe der Zeitschrift
- 17
Datenquelle: Europe PubMed Central
- Abstract
- Trinuclear ferrocene tris-amides were synthesized from an Fmoc- or Boc-protected ferrocene amino acid, and hydrogen-bonded zigzag conformations were determined by NMR spectroscopy, molecular modelling, and X-ray diffraction. In these ordered secondary structures orientation of the individual amide dipole moments approximately in the same direction results in a macrodipole moment similar to that of α-helices composed of α-amino acids. Unlike ordinary α-amino acids, the building blocks in these ferrocene amides with defined secondary structure can be sequentially oxidized to mono-, di-, and trications. Singly and doubly charged mixed-valent cations were probed experimentally by Vis/NIR, paramagnetic ¹H NMR and Mössbauer spectroscopy and investigated theoretically by DFT calculations. According to the appearance of intervalence charge transfer (IVCT) bands in solution, the ferrocene/ferrocenium amides are described as Robin-Day class II mixed-valent systems. Mössbauer spectroscopy indicates trapped valences in the solid state. The secondary structure of trinuclear ferrocene tris-amides remains intact (coiled form) upon oxidation to mono- and dications according to DFT calculations, while oxidation to the trication should break the intramolecular hydrogen bonding and unfold the ferrocene peptide (uncoiled form).
- Autoren
- Daniel Siebler
- Michael Linseis
- Teuta Gasi
- Luca M Carrella
- Rainer F Winter
- Christoph Förster
- Katja Heinze
- Autoren-URL
- https://www.ncbi.nlm.nih.gov/pubmed/21274954
- DOI
- 10.1002/chem.201002101
- eISSN
- 1521-3765
- Ausgabe der Veröffentlichung
- 16
- Zeitschrift
- Chemistry
- Schlüsselwörter
- Amides
- Ferrous Compounds
- Magnetic Resonance Spectroscopy
- Metallocenes
- Models, Molecular
- Molecular Conformation
- Molecular Structure
- Oxidation-Reduction
- Peptides
- Sprache
- eng
- Country
- Germany
- Paginierung
- 4540 - 4551
- Datum der Veröffentlichung
- 2011
- Status
- Published
- Datum, an dem der Datensatz öffentlich gemacht wurde
- 2011
- Titel
- Oligonuclear ferrocene amides: mixed-valent peptides and potential redox-switchable foldamers.
- Sub types
- Journal Article
- Research Support, Non-U.S. Gov't
- Ausgabe der Zeitschrift
- 17
Datenquelle: PubMed
- Beziehungen:
-