DNA-catalyzed hydrolysis of esters and aromatic amides

Benjamin M. Brandsen, Anthony R. Hesser, Marissa A. Castner, Madhavaiah Chandra, Scott K Silverman

Research output: Contribution to journalArticle

Abstract

We previously reported that DNA catalysts (deoxyribozymes) can hydrolyze DNA phosphodiester linkages, but DNA-catalyzed amide bond hydrolysis has been elusive. Here we used in vitro selection to identify DNA catalysts that hydrolyze ester linkages as well as DNA catalysts that hydrolyze aromatic amides, for which the leaving group is an aniline moiety. The aromatic amide-hydrolyzing deoxyribozymes were examined using linear free energy relationship analysis. The hydrolysis reaction is unaffected by substituents on the aromatic ring (ρ ≈ 0), suggesting general acid-catalyzed elimination as the likely rate-determining step of the addition-elimination hydrolysis mechanism. These findings establish that DNA has the catalytic ability to achieve hydrolysis of esters and aromatic amides as carbonyl-based substrates, and they suggest a mechanism-based approach to achieve DNA-catalyzed aliphatic amide hydrolysis.

Original languageEnglish (US)
Pages (from-to)16014-16017
Number of pages4
JournalJournal of the American Chemical Society
Volume135
Issue number43
DOIs
StatePublished - Oct 30 2013

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Amides
ester
hydrolysis
Hydrolysis
Esters
DNA
Catalytic DNA
catalyst
Catalysts
Aniline
Free energy
Acids
substrate
acid
Substrates
energy

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

DNA-catalyzed hydrolysis of esters and aromatic amides. / Brandsen, Benjamin M.; Hesser, Anthony R.; Castner, Marissa A.; Chandra, Madhavaiah; Silverman, Scott K.

In: Journal of the American Chemical Society, Vol. 135, No. 43, 30.10.2013, p. 16014-16017.

Research output: Contribution to journalArticle

Brandsen, BM, Hesser, AR, Castner, MA, Chandra, M & Silverman, SK 2013, 'DNA-catalyzed hydrolysis of esters and aromatic amides', Journal of the American Chemical Society, vol. 135, no. 43, pp. 16014-16017. https://doi.org/10.1021/ja4077233
Brandsen, Benjamin M. ; Hesser, Anthony R. ; Castner, Marissa A. ; Chandra, Madhavaiah ; Silverman, Scott K. / DNA-catalyzed hydrolysis of esters and aromatic amides. In: Journal of the American Chemical Society. 2013 ; Vol. 135, No. 43. pp. 16014-16017.
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