Cooperative assembly of Zn cross-linked artificial tripeptides with pendant hydroxyquinoline ligands

Meng Zhang, Joy A. Gallagher, Matthew B. Coppock, Lisa M. Pantzar, Mary Elizabeth Williams

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

An artificial peptide with three pendant hydroxyquinoline (hq) ligands on a palindromic backbone was designed and used to form multimetallic assemblies. Reaction of the tripeptide with zinc acetate led to a highly fluorescent tripeptide duplex with three Zn(II) coordinative cross-links. The binding process was monitored using spectrophotometric absorbance and emission titrations; NMR spectroscopy and mass spectrometry confirmed the identity and stoichiometry of the product structure. Titrations monitoring duplex formation of the zinc-tripeptide structure had a sigmoidal shape, equilibrium constant larger than the monomeric analogue, and a Hill coefficient >1, all of which indicate positive cooperativity. Photophysical characterization of the quantum yield, excited state lifetime, and polarization anisotropy are compared with the monometallic zinc-hq analogue. A higher than expected quantum yield for the trimetallic complex suggests a structure in which the central chromophore is shielded from solvent by π-stacking with neighboring Zn(II) complexes.

Original languageEnglish (US)
Pages (from-to)11315-11323
Number of pages9
JournalInorganic Chemistry
Volume51
Issue number21
DOIs
StatePublished - Nov 5 2012

Fingerprint

Hydroxyquinolines
Quantum yield
Titration
Zinc
Zinc Acetate
assembly
zinc
Ligands
titration
ligands
Equilibrium constants
Chromophores
Excited states
lead acetates
Stoichiometry
analogs
Nuclear magnetic resonance spectroscopy
Mass spectrometry
Anisotropy
Polarization

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Zhang, Meng ; Gallagher, Joy A. ; Coppock, Matthew B. ; Pantzar, Lisa M. ; Williams, Mary Elizabeth. / Cooperative assembly of Zn cross-linked artificial tripeptides with pendant hydroxyquinoline ligands. In: Inorganic Chemistry. 2012 ; Vol. 51, No. 21. pp. 11315-11323.
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abstract = "An artificial peptide with three pendant hydroxyquinoline (hq) ligands on a palindromic backbone was designed and used to form multimetallic assemblies. Reaction of the tripeptide with zinc acetate led to a highly fluorescent tripeptide duplex with three Zn(II) coordinative cross-links. The binding process was monitored using spectrophotometric absorbance and emission titrations; NMR spectroscopy and mass spectrometry confirmed the identity and stoichiometry of the product structure. Titrations monitoring duplex formation of the zinc-tripeptide structure had a sigmoidal shape, equilibrium constant larger than the monomeric analogue, and a Hill coefficient >1, all of which indicate positive cooperativity. Photophysical characterization of the quantum yield, excited state lifetime, and polarization anisotropy are compared with the monometallic zinc-hq analogue. A higher than expected quantum yield for the trimetallic complex suggests a structure in which the central chromophore is shielded from solvent by π-stacking with neighboring Zn(II) complexes.",
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Cooperative assembly of Zn cross-linked artificial tripeptides with pendant hydroxyquinoline ligands. / Zhang, Meng; Gallagher, Joy A.; Coppock, Matthew B.; Pantzar, Lisa M.; Williams, Mary Elizabeth.

In: Inorganic Chemistry, Vol. 51, No. 21, 05.11.2012, p. 11315-11323.

Research output: Contribution to journalArticle

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AU - Zhang, Meng

AU - Gallagher, Joy A.

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AU - Williams, Mary Elizabeth

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AB - An artificial peptide with three pendant hydroxyquinoline (hq) ligands on a palindromic backbone was designed and used to form multimetallic assemblies. Reaction of the tripeptide with zinc acetate led to a highly fluorescent tripeptide duplex with three Zn(II) coordinative cross-links. The binding process was monitored using spectrophotometric absorbance and emission titrations; NMR spectroscopy and mass spectrometry confirmed the identity and stoichiometry of the product structure. Titrations monitoring duplex formation of the zinc-tripeptide structure had a sigmoidal shape, equilibrium constant larger than the monomeric analogue, and a Hill coefficient >1, all of which indicate positive cooperativity. Photophysical characterization of the quantum yield, excited state lifetime, and polarization anisotropy are compared with the monometallic zinc-hq analogue. A higher than expected quantum yield for the trimetallic complex suggests a structure in which the central chromophore is shielded from solvent by π-stacking with neighboring Zn(II) complexes.

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