Abstract

As a type of safe, clean, and bio-relevant oxidant, hydrogen peroxide has been widely used as a trigger in the design of stimuli-responsive materials. Hindered urea bond (HUB) is a type of dynamic covalent bond which can reversibly dissociate into isocyanate and amine. Quenching of isocyanate or amine will shift the equilibrium and facilitate the degradation of HUB bond. Herein, we report that one of the HUB moiety – 1,1-tert-butylethylurea (TBEU) can react with hydrogen peroxide (H 2 O 2 ) resulting in two opposing outcomes. Perhydrolysis of isocyanate and oxidation of amine lead to the bond fracture, while formation of urethane product with an oxygen inserted into the original TBEU structure was also observed giving a stabilized form of linkage. More precise kinetic control of the two distinct pathways are expected to make hydrogen peroxide a trigger to either degrade or fix the HUB based polymeric materials.

Original languageEnglish (US)
Pages (from-to)728-731
Number of pages4
JournalEuropean Journal of Organic Chemistry
Volume2019
Issue number4
DOIs
StatePublished - Jan 1 2019

Fingerprint

hydrogen peroxide
ureas
Isocyanates
Hydrogen Peroxide
isocyanates
Urea
chemistry
Amines
amines
actuators
urethanes
Covalent bonds
Urethane
covalent bonds
Oxidants
linkages
fixing
stimuli
Quenching
quenching

Keywords

  • Degradation
  • Dynamic covalent bond
  • Hindered urea
  • Hydrogen peroxide
  • Stabilization

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

Hindered urea bond : A bilaterally responsive chemistry to hydrogen peroxide. / Ying, Hanze; Yang, Yingfeng; Cai, Kaimin; Cheng, Jianjun.

In: European Journal of Organic Chemistry, Vol. 2019, No. 4, 01.01.2019, p. 728-731.

Research output: Contribution to journalArticle

Ying, Hanze ; Yang, Yingfeng ; Cai, Kaimin ; Cheng, Jianjun. / Hindered urea bond : A bilaterally responsive chemistry to hydrogen peroxide. In: European Journal of Organic Chemistry. 2019 ; Vol. 2019, No. 4. pp. 728-731.
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AB - As a type of safe, clean, and bio-relevant oxidant, hydrogen peroxide has been widely used as a trigger in the design of stimuli-responsive materials. Hindered urea bond (HUB) is a type of dynamic covalent bond which can reversibly dissociate into isocyanate and amine. Quenching of isocyanate or amine will shift the equilibrium and facilitate the degradation of HUB bond. Herein, we report that one of the HUB moiety – 1,1-tert-butylethylurea (TBEU) can react with hydrogen peroxide (H 2 O 2 ) resulting in two opposing outcomes. Perhydrolysis of isocyanate and oxidation of amine lead to the bond fracture, while formation of urethane product with an oxygen inserted into the original TBEU structure was also observed giving a stabilized form of linkage. More precise kinetic control of the two distinct pathways are expected to make hydrogen peroxide a trigger to either degrade or fix the HUB based polymeric materials.

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