A pH-triggered polymer degradation or drug delivery system by light-mediated cis/trans isomerization of o-hydroxy cinnamates

A new methodology for the pH-triggered degradation of polymers or for therelease of drugs under visible light irradiation based on the cyclization ofortho-hydroxy-cinnamates (oHC) to coumarins is described. The key oHCstructural motif can be readily incorporated into the rational design of novelphot...

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Bibliographic Details
Authors: Díaz Díaz, David, Abramov, Alex, Maiti, Binoy, Keridou, Ina, Puiggalí, Jordi, Reiser, Oliver
Format: article
Status:Published version
Publication Date:2021
Country:España
Institution:Universidad de La Laguna (ULL)
Repository:RIULL. Repositorio Institucional de la Universidad de La Laguna
OAI Identifier:oai:riull.ull.es:915/42193
Online Access:http://riull.ull.es/xmlui/handle/915/42193
Access Level:Open access
Keyword:Polymer degradation
Cis/Trans isomerization
o-Hydroxy cinnamates
drugs
visible light irradiation
Description
Summary:A new methodology for the pH-triggered degradation of polymers or for therelease of drugs under visible light irradiation based on the cyclization ofortho-hydroxy-cinnamates (oHC) to coumarins is described. The key oHCstructural motif can be readily incorporated into the rational design of novelphotocleavable polymers via click chemistry. This main-chain moietyundergoes a fast photocleavage when irradiated with 455 nm light providedthat a suitable base is added. A series of polyethylene glycol-alt-ortho-hydroxycinnamate (polyethylene glycol (PEG)n-alt-oHC)-based polymers aresynthesized and the time-dependent visible-light initiated cleavage of thephotoactive monomer and polymer is investigated in solution by a variety ofspectroscopic and chromatographic techniques. The photo-degradationbehavior of the water-soluble poly(PEG2000 -alt-oHC) is investigated within abroad pH range (pH = 2.1–11.8), demonstrating fast degradation at pH 11.8,while the stability of the polymer is greatly enhanced at pH 2.1. Moreover, theneat polymer shows long-term stability under daylight conditions, thusallowing its storage without special precautions. In addition, twowater-soluble PEG-based drug-carrier molecules(mPEG 2000 -oHC-benzhydrol/phenol) are synthesized and used for drugdelivery studies, monitoring the process by UV–vis spectroscopy in anON/OFF intermittent manner.