Products Cited in Publications Worldwide Depolymerization of penicillamine and 4-hydroxyproline based polythioesters in organic and aqueous solution

Depolymerization of penicillamine and 4-hydroxyproline based polythioesters in organic and aqueous solution

Shen, Chenfangfei; Tamminga, Micah J; Gillies, Elizabeth R

DOI:

Abstract

There is growing interest in self-immolative polymers (SIPs), which can depolymerize end-to-end in response to backbone or end-cap cleavage. The ability of these polymers to respond to specific stimuli has garnered interest for a wide range of applications, including drug and nucleic acid delivery, sensing, micro- and nanoscale patterning, adhesives, and recyclable plastics. Among the promising candidates for SIPs are polythioesters (PTEs), which feature dynamic thioester bonds in their backbone. Despite recent advancements, investigation into the depolymerization behavior of PTEs in aqueous environments remains limited. Herein, we explore the behavior of two different PTE backbones. PTEs based on D-penicillamine and Boc-L-hydroxyproline were synthesized with disulfide and control end-caps. The penicillamine-based polymers depolymerized in response to dithiothreitol (DTT) regardless of their end-cap, indicating that DTT could cleave the polymer backbone, which could be followed by depolymerization and additional backbone cleavage events. On the other hand, the dominant mechanism for the hydroxyproline-based polythioesters appeared to be end-cap cleavage, followed by depolymerization. Overall, both classes of PTEs were responsive to thiols, indicating their potential utility in biomedical conditions involving hypoxia, and thus elevated levels of thiols such as glutathione. As proof of concept, we also demonstrated that the PTEs could be used to prepare degradable gels and self-assembled nanoparticles.

Keywords

Polythioester ; Self-immolative ; Depolymerization ; Reduction-responsive

Purchased from AmBeed

Penicillamine

A10138952-67-598%

Penicillamine

10.0/50mg

Detail
Tetraethylene glycol monomethyl ether

A24018623783-42-898%

Tetraethylene glycol monomethyl ether

12.0/5g

Detail
Boc-trans-D-Hyp-OH

A340068147266-92-097%

Boc-trans-D-Hyp-OH

61.0/25g

Detail
DTT

A5876353483-12-395%

DTT

634.0/500g

Detail
Magnesium sulfate

A8829317487-88-998%

Magnesium sulfate

10.0/25g

Detail