Self-Sorting of Cyclic Peptide Homodimers into a Heterodimeric Assembly Featuring an Efficient Photoinduced Intramolecular Electron-Transfer Process (Articolo in rivista)

Type

• Articolo in rivista (Classe)
• Prodotto della ricerca (Classe)

Label

• Self-Sorting of Cyclic Peptide Homodimers into a Heterodimeric Assembly Featuring an Efficient Photoinduced Intramolecular Electron-Transfer Process (Articolo in rivista) (literal)

Anno

• 2014-01-01T00:00:00+01:00 (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi

• 10.1002/chem.201304200 (literal)

Alternative label

• Aragay, Gemma; Ventura, Barbara; Guerra, Arcadio; Pintre, Inmaculada; Chiorboli, Claudio; Garcia-Fandino, Rebeca; Flamigni, Lucia; Granja, Juan R.; Ballester, Pablo (2014)
  Self-Sorting of Cyclic Peptide Homodimers into a Heterodimeric Assembly Featuring an Efficient Photoinduced Intramolecular Electron-Transfer Process
  in Chemistry (Weinh., Print)
  (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori

• Aragay, Gemma; Ventura, Barbara; Guerra, Arcadio; Pintre, Inmaculada; Chiorboli, Claudio; Garcia-Fandino, Rebeca; Flamigni, Lucia; Granja, Juan R.; Ballester, Pablo (literal)

Pagina inizio

• 3427 (literal)

Pagina fine

• 3438 (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume

• 20 (literal)

Rivista

• Chemistry (Rivista)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#pagineTotali

• 12 (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroFascicolo

• 12 (literal)

Note

• ISI Web of Science (WOS) (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni

• Institute of Chemical Research of Catalonia; Catalan Inst Res & Adv Studies ICREA; Ist ISOF CNR; Univ Santiago (literal)

Titolo

• Self-Sorting of Cyclic Peptide Homodimers into a Heterodimeric Assembly Featuring an Efficient Photoinduced Intramolecular Electron-Transfer Process (literal)

Abstract

• We describe the thermodynamic characterisation of the self-sorting process experienced by two homodimers assembled by hydrogen-bonding interactions through their cyclopeptide scaffolds and decorated with Zn-porphyrin and fullerene units into a heterodimeric assembly that contains one electron-donor (Zn-porphyrin) and one electron-acceptor group (fullerene). The fluorescence of the Zn-porphyrin unit is strongly quenched upon heterodimer formation. This phenomenon is demonstrated to be the result of an efficient photoinduced electron-transfer (PET) process occurring between the Zn-porphyrin and the fullerene units of the heterodimeric system. The recombination lifetime of the charge-separated state of the heterodimer complex is in the order of 180ns. In solution, both homo- and heterodimers are present as a mixture of three regioisomers: two staggered and one eclipsed. At the concentration used for this study, the high stability constant determined for the heterodimer suggests that the eclipsed conformer is the main component in solution. The application of the bound-state scenario allowed us to calculate that the heterodimer exists mainly as the eclipsed regioisomer (75-90%). The attractive interaction that exists between the donor and acceptor chromophores in the heterodimeric assembly favours their arrangement in close contact. This is confirmed by the presence of charge-transfer bands centred at 720nm in the absorption spectrum of the heterodimer. PET occurs in approximately 75% of the chromophores after excitation of both Zn-porphyrin and fullerene chromophores. Conversely, analogous systems, reported previously, decorated with extended tetrathiafulvalene and fullerene units showed a PET process in a significantly reduced extent (33%). We conclude that the strength (stability constant (K)xeffective molarity (EM)) of the intramolecular interaction established between the two chromophores in the Zn-porphyrin/fullerene cyclopeptide-based heterodimers controls the regioisomeric distribution and regulates the high extent to which the PET process takes place in this system. (literal)

Prodotto di

• Materiali Avanzati per la COnversione di energia Luminosa (MACOL) (PM.P04.010.001) (Modulo)
• Institute for organic syntheses and photoreactivity (ISOF) (Istituto)

Autore CNR

• CLAUDIO CHIORBOLI (Unità di personale interno)
• BARBARA VENTURA (Persona)
• LUCIA FLAMIGNI (Unità di personale interno)

Insieme di parole chiave

• Keywords of "Self-Sorting of Cyclic Peptide Homodimers into a Heterodimeric Assembly Featuring an Efficient Photoinduced Intramolecular Electron-Transfer Process" (Insieme di parole chiave)

Incoming links:

Prodotto

• Institute for organic syntheses and photoreactivity (ISOF) (Istituto)
• Materiali Avanzati per la COnversione di energia Luminosa (MACOL) (PM.P04.010.001) (Modulo)

Autore CNR di

• LUCIA FLAMIGNI (Unità di personale interno)
• CLAUDIO CHIORBOLI (Unità di personale interno)
• BARBARA VENTURA (Persona)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#rivistaDi

• Chemistry (Rivista)

Insieme di parole chiave di

• Keywords of "Self-Sorting of Cyclic Peptide Homodimers into a Heterodimeric Assembly Featuring an Efficient Photoinduced Intramolecular Electron-Transfer Process" (Insieme di parole chiave)