Investigations of metal-coordinated peptides as supramolecular synthons

Warren W. Gerhardt, Marcus Weck

Research output: Contribution to journalArticle

Abstract

This article describes the synthesis and controlled assembly of four model biological-hybrid scaffolds via coordination of a metal complex to four new tripeptides. Each model tripeptide investigated has either a central pyridyl glycyl or a pyridyl alanyl residue between two terminally protected glycines. All tripeptides were coordinated to their complementary recognition unit, a p-methoxy SCS-Pd pincer complex. The assembly events were fully characterized and investigated by 1H NMR, ES-MS, and isothermal titration calorimetry (ITC) to elucidate how the substitution and spatial distance of the pyridyl moiety to the peptide backbone affects the metal coordination. Using these characterization techniques, we have shown that the metal-coordination events in all cases are fast and quantitative and that the peptide backbones do not interfere with the self-assembly. The ITC analyses showed that the 4-pyridyl tripeptides are the tightest binding ligands toward the palladated pincer complexes with the alanyl derivative being the strongest overall, demonstrating the superiority of the 4-pyridyl peptides over their 3-pyridyl analogues. The measured association constants are comparable to other pincer-pyridine systems in DMSO suggesting that the controlled coordination of the metalated pincer/pyridine interaction is an interesting biological synthon and will allow for the future development of important noncovalent peptide-based hybrid materials.

Original languageEnglish (US)
Pages (from-to)6333-6341
Number of pages9
JournalJournal of Organic Chemistry
Volume71
Issue number17
DOIs
StatePublished - Aug 18 2006

Fingerprint

Metals
Peptides
Calorimetry
Titration
Coordination Complexes
Hybrid materials
Dimethyl Sulfoxide
Scaffolds
Glycine
Self assembly
Substitution reactions
Nuclear magnetic resonance
Association reactions
Ligands
Derivatives
pyridine

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Investigations of metal-coordinated peptides as supramolecular synthons. / Gerhardt, Warren W.; Weck, Marcus.

In: Journal of Organic Chemistry, Vol. 71, No. 17, 18.08.2006, p. 6333-6341.

Research output: Contribution to journalArticle

@article{e97b5ef39a76453a98e942240a40f368,
title = "Investigations of metal-coordinated peptides as supramolecular synthons",
abstract = "This article describes the synthesis and controlled assembly of four model biological-hybrid scaffolds via coordination of a metal complex to four new tripeptides. Each model tripeptide investigated has either a central pyridyl glycyl or a pyridyl alanyl residue between two terminally protected glycines. All tripeptides were coordinated to their complementary recognition unit, a p-methoxy SCS-Pd pincer complex. The assembly events were fully characterized and investigated by 1H NMR, ES-MS, and isothermal titration calorimetry (ITC) to elucidate how the substitution and spatial distance of the pyridyl moiety to the peptide backbone affects the metal coordination. Using these characterization techniques, we have shown that the metal-coordination events in all cases are fast and quantitative and that the peptide backbones do not interfere with the self-assembly. The ITC analyses showed that the 4-pyridyl tripeptides are the tightest binding ligands toward the palladated pincer complexes with the alanyl derivative being the strongest overall, demonstrating the superiority of the 4-pyridyl peptides over their 3-pyridyl analogues. The measured association constants are comparable to other pincer-pyridine systems in DMSO suggesting that the controlled coordination of the metalated pincer/pyridine interaction is an interesting biological synthon and will allow for the future development of important noncovalent peptide-based hybrid materials.",
author = "Gerhardt, {Warren W.} and Marcus Weck",
year = "2006",
month = "8",
day = "18",
doi = "10.1021/jo060395q",
language = "English (US)",
volume = "71",
pages = "6333--6341",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "17",

}

TY - JOUR

T1 - Investigations of metal-coordinated peptides as supramolecular synthons

AU - Gerhardt, Warren W.

AU - Weck, Marcus

PY - 2006/8/18

Y1 - 2006/8/18

N2 - This article describes the synthesis and controlled assembly of four model biological-hybrid scaffolds via coordination of a metal complex to four new tripeptides. Each model tripeptide investigated has either a central pyridyl glycyl or a pyridyl alanyl residue between two terminally protected glycines. All tripeptides were coordinated to their complementary recognition unit, a p-methoxy SCS-Pd pincer complex. The assembly events were fully characterized and investigated by 1H NMR, ES-MS, and isothermal titration calorimetry (ITC) to elucidate how the substitution and spatial distance of the pyridyl moiety to the peptide backbone affects the metal coordination. Using these characterization techniques, we have shown that the metal-coordination events in all cases are fast and quantitative and that the peptide backbones do not interfere with the self-assembly. The ITC analyses showed that the 4-pyridyl tripeptides are the tightest binding ligands toward the palladated pincer complexes with the alanyl derivative being the strongest overall, demonstrating the superiority of the 4-pyridyl peptides over their 3-pyridyl analogues. The measured association constants are comparable to other pincer-pyridine systems in DMSO suggesting that the controlled coordination of the metalated pincer/pyridine interaction is an interesting biological synthon and will allow for the future development of important noncovalent peptide-based hybrid materials.

AB - This article describes the synthesis and controlled assembly of four model biological-hybrid scaffolds via coordination of a metal complex to four new tripeptides. Each model tripeptide investigated has either a central pyridyl glycyl or a pyridyl alanyl residue between two terminally protected glycines. All tripeptides were coordinated to their complementary recognition unit, a p-methoxy SCS-Pd pincer complex. The assembly events were fully characterized and investigated by 1H NMR, ES-MS, and isothermal titration calorimetry (ITC) to elucidate how the substitution and spatial distance of the pyridyl moiety to the peptide backbone affects the metal coordination. Using these characterization techniques, we have shown that the metal-coordination events in all cases are fast and quantitative and that the peptide backbones do not interfere with the self-assembly. The ITC analyses showed that the 4-pyridyl tripeptides are the tightest binding ligands toward the palladated pincer complexes with the alanyl derivative being the strongest overall, demonstrating the superiority of the 4-pyridyl peptides over their 3-pyridyl analogues. The measured association constants are comparable to other pincer-pyridine systems in DMSO suggesting that the controlled coordination of the metalated pincer/pyridine interaction is an interesting biological synthon and will allow for the future development of important noncovalent peptide-based hybrid materials.

UR - http://www.scopus.com/inward/record.url?scp=33747411805&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33747411805&partnerID=8YFLogxK

U2 - 10.1021/jo060395q

DO - 10.1021/jo060395q

M3 - Article

C2 - 16901113

AN - SCOPUS:33747411805

VL - 71

SP - 6333

EP - 6341

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 17

ER -