Photoinduced Cleavage and Hydrolysis of o-Nitrobenzyl Linker and Covalent Linker Immobilization in Gelatin Methacryloyl Hydrogels

Macromol Biosci. 2018 Sep;18(9):e1800104. doi: 10.1002/mabi.201800104. Epub 2018 Jun 26.

Abstract

Light-induced release systems can be triggered remotely and are of interest for many controlled release applications due to the possibility for spatio-temporal release control. In this study a biotin-functionalized photocleavable macromer is incorporated with an o-nitrobenzyl moiety into gelatin methacryloyl(-acetyl) hydrogels via radical cross-linking. Stronger immobilization of streptavidin-coupled horseradish peroxidase occurs in linker-functionalized hydrogels compared to pure gelatin methacryloyl(-acetyl) hydrogels, and a controlled release of the streptavidin conjugate upon UV-irradiation is possible. Liquid chromatography coupled to mass spectrometry (LC-MS) analysis of aqueous linker solutions allows the identification of the main cleavage products and the cleavage kinetics. Thus, it is shown that a significant hydrolysis of the linker occurs at 37 °C. Nevertheless the system reported here is a promising controlled release scaffold for proteins and application in tissue engineering, if background releases of the immobilized drug are tolerable.

Keywords: LC-MS; gelatin methacryloyl; photocleavable linker; stimuli-responsive release; streptavidin-coupled HRP.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Chromatography, Liquid
  • Enzymes, Immobilized / chemistry
  • Enzymes, Immobilized / pharmacokinetics*
  • Gelatin / chemistry*
  • Horseradish Peroxidase / chemistry
  • Horseradish Peroxidase / pharmacokinetics
  • Hydrogels / chemistry*
  • Hydrolysis
  • Mass Spectrometry
  • Methacrylates / chemistry*
  • Photochemistry / methods
  • Solutions / chemistry
  • Streptavidin / chemistry
  • Ultraviolet Rays

Substances

  • Enzymes, Immobilized
  • Hydrogels
  • Methacrylates
  • Solutions
  • Gelatin
  • Streptavidin
  • Horseradish Peroxidase