Bioconjugation with Thiols by Benzylic Substitution

Kenji Watanabe, Takashi Ohshima

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

A benzylic substitution of 3-indolyl(hydroxyl)acetate derivatives with thiols proceeded specifically in the presence of amino, carboxy, and phosphate groups in weakly acidic aqueous solutions under nearly physiological condition, while no reaction occurred at pH over 7. Kinetic studies revealed that the reaction followed second-order kinetics (first-order in the reactant and first-order in thiol) in contrast with the SN1 mechanism of common benzylic substitution of alcohols. The utility of the present method for functionalization of biomacromolecules was demonstrated using several model proteins, such as lysozyme, insulin, trypsin, and serum albumin. The catalytic bioactivity of lysozyme in lysis of Micrococcus lysodeikticus cells was completely retained after the modification.

Original languageEnglish
Pages (from-to)3959-3964
Number of pages6
JournalChemistry - A European Journal
Volume24
Issue number16
DOIs
Publication statusPublished - Mar 15 2018

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Muramidase
Sulfhydryl Compounds
Substitution reactions
Enzymes
Kinetics
Insulin
Bioactivity
Serum Albumin
Hydroxyl Radical
Trypsin
Phosphates
Acetates
Alcohols
Derivatives
Proteins
carboxy phosphate

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

Cite this

Bioconjugation with Thiols by Benzylic Substitution. / Watanabe, Kenji; Ohshima, Takashi.

In: Chemistry - A European Journal, Vol. 24, No. 16, 15.03.2018, p. 3959-3964.

Research output: Contribution to journalArticle

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