Protonation of carboxyl groups in EuDOTA-tetraamide complexes results in catalytic prototropic exchange and quenching of the CEST signal

Lei Zhang, Osasere M. Evbuomwan, Michael Tieu, Piyu Zhao, Andre F. Martins, A. Dean Sherry

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

The CEST properties of EuDOTA-tetraamide complexes bearing pendant carboxylate and carboxyl ethyl esters were measured as a function of pH. The CEST signal from the Eu3+-bound water molecule decreased in intensity between pH 8.5 and 4.5 while the proton exchange rates (kex) increased over this same pH range. In comparison, the CEST signal in the corresponding carboxyl ester derivatives was nearly constant. Both observations are consistent with stepwise protonation of the four carboxylic acid groups over this same pH range. This indicates that negative charges on the carboxyl groups above pH 6 facilitate the formation of a strong hydrogen-bonding network in the coordination second sphere above the single Eu3+-bound water molecule, thereby decreasing prototropic exchange of protons on the bound water molecule with bulk water protons. The percentage of square antiprismatic versus twisted square antiprism coordination isomers also decreased as the appended carboxylic acid groups were positioned further away from the amide. The net effect of lowering the pH was an overall increase in kex and a quenching of the CEST signal. This article is part of the themed issue ‘Challenges for chemistry in molecular imaging’.

Original languageEnglish (US)
Article number20170113
JournalPhilosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences
Volume375
Issue number2107
DOIs
StatePublished - Nov 28 2017

Fingerprint

Protonation
carboxyl group
Quenching
quenching
Water
Protons
Molecules
Carboxylic acids
Square antiprism
Ion exchange
Esters
Bearings (structural)
Molecular imaging
carboxylic acids
water
protons
esters
Exchange rate
Amides
Isomers

Keywords

  • Eu complex
  • MRI contrast agent
  • PH sensor

ASJC Scopus subject areas

  • Mathematics(all)
  • Engineering(all)
  • Physics and Astronomy(all)

Cite this

Protonation of carboxyl groups in EuDOTA-tetraamide complexes results in catalytic prototropic exchange and quenching of the CEST signal. / Zhang, Lei; Evbuomwan, Osasere M.; Tieu, Michael; Zhao, Piyu; Martins, Andre F.; Sherry, A. Dean.

In: Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 375, No. 2107, 20170113, 28.11.2017.

Research output: Contribution to journalArticle

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