Transformation of RAFT polymer end groups into nitric oxide donor moieties: en route to biochemically active nanostructures

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Abstract

Polymers with a terminal S-nitrosothiol moiety were synthesized by modifying the thiocarbonylthio end group formed by reversible addition-fragmentation chain transfer polymerization. Specifically, benzodithioate-terminated poly[oligo(ethylene glycol) methyl ether methacrylate] (POEGMA) was first synthesized by polymerizing OEGMA in the presence of 4-cyano-4-(phenylcarbonothioylthio)pentanoic acid. Sequential treatment with hydrazine hydrate and a stoichiometric amount of nitrous acid resulted in the formation of S-nitrosothiol-terminated polymers. A similar approach was applied to block copolymers of POEGMA incorporating a domain of poly[(N,N-diisopropylamino)ethyl methacrylate], thus, enabling the preparation of pH responsive nitric oxide (NO)-releasing micelles. The micelles possessed substantially modified S-nitrosothiol loss kinetics compared to the hydrophilic homopolymer analogue. Moreover, thiol-triggered degradation of the S-nitrosothiol was significantly slower when the S-nitrosothiol was embedded in a micellar structure. These results demonstrate that it is possible to incorporate nitric oxide donor moieties directly onto a polymer chain end, enabling simple synthesis of biochemically active nanostructures.
Original languageEnglish
Pages (from-to)1278-1282
Number of pages5
JournalACS Macro Letters
Volume4
Issue number11
DOIs
Publication statusPublished - 2015

Cite this

@article{96c9b5bb14f54e32a57a9c4bb314bbf4,
title = "Transformation of RAFT polymer end groups into nitric oxide donor moieties: en route to biochemically active nanostructures",
abstract = "Polymers with a terminal S-nitrosothiol moiety were synthesized by modifying the thiocarbonylthio end group formed by reversible addition-fragmentation chain transfer polymerization. Specifically, benzodithioate-terminated poly[oligo(ethylene glycol) methyl ether methacrylate] (POEGMA) was first synthesized by polymerizing OEGMA in the presence of 4-cyano-4-(phenylcarbonothioylthio)pentanoic acid. Sequential treatment with hydrazine hydrate and a stoichiometric amount of nitrous acid resulted in the formation of S-nitrosothiol-terminated polymers. A similar approach was applied to block copolymers of POEGMA incorporating a domain of poly[(N,N-diisopropylamino)ethyl methacrylate], thus, enabling the preparation of pH responsive nitric oxide (NO)-releasing micelles. The micelles possessed substantially modified S-nitrosothiol loss kinetics compared to the hydrophilic homopolymer analogue. Moreover, thiol-triggered degradation of the S-nitrosothiol was significantly slower when the S-nitrosothiol was embedded in a micellar structure. These results demonstrate that it is possible to incorporate nitric oxide donor moieties directly onto a polymer chain end, enabling simple synthesis of biochemically active nanostructures.",
author = "Yu, {Sul Hwa} and Jinming Hu and Francesca Ercole and Truong, {Nghia P} and Davis, {Thomas P} and Whittaker, {Michael R} and Quinn, {John F}",
year = "2015",
doi = "10.1021/acsmacrolett.5b00733",
language = "English",
volume = "4",
pages = "1278--1282",
journal = "ACS Macro Letters",
issn = "2161-1653",
publisher = "American Chemical Society",
number = "11",

}

TY - JOUR

T1 - Transformation of RAFT polymer end groups into nitric oxide donor moieties: en route to biochemically active nanostructures

AU - Yu, Sul Hwa

AU - Hu, Jinming

AU - Ercole, Francesca

AU - Truong, Nghia P

AU - Davis, Thomas P

AU - Whittaker, Michael R

AU - Quinn, John F

PY - 2015

Y1 - 2015

N2 - Polymers with a terminal S-nitrosothiol moiety were synthesized by modifying the thiocarbonylthio end group formed by reversible addition-fragmentation chain transfer polymerization. Specifically, benzodithioate-terminated poly[oligo(ethylene glycol) methyl ether methacrylate] (POEGMA) was first synthesized by polymerizing OEGMA in the presence of 4-cyano-4-(phenylcarbonothioylthio)pentanoic acid. Sequential treatment with hydrazine hydrate and a stoichiometric amount of nitrous acid resulted in the formation of S-nitrosothiol-terminated polymers. A similar approach was applied to block copolymers of POEGMA incorporating a domain of poly[(N,N-diisopropylamino)ethyl methacrylate], thus, enabling the preparation of pH responsive nitric oxide (NO)-releasing micelles. The micelles possessed substantially modified S-nitrosothiol loss kinetics compared to the hydrophilic homopolymer analogue. Moreover, thiol-triggered degradation of the S-nitrosothiol was significantly slower when the S-nitrosothiol was embedded in a micellar structure. These results demonstrate that it is possible to incorporate nitric oxide donor moieties directly onto a polymer chain end, enabling simple synthesis of biochemically active nanostructures.

AB - Polymers with a terminal S-nitrosothiol moiety were synthesized by modifying the thiocarbonylthio end group formed by reversible addition-fragmentation chain transfer polymerization. Specifically, benzodithioate-terminated poly[oligo(ethylene glycol) methyl ether methacrylate] (POEGMA) was first synthesized by polymerizing OEGMA in the presence of 4-cyano-4-(phenylcarbonothioylthio)pentanoic acid. Sequential treatment with hydrazine hydrate and a stoichiometric amount of nitrous acid resulted in the formation of S-nitrosothiol-terminated polymers. A similar approach was applied to block copolymers of POEGMA incorporating a domain of poly[(N,N-diisopropylamino)ethyl methacrylate], thus, enabling the preparation of pH responsive nitric oxide (NO)-releasing micelles. The micelles possessed substantially modified S-nitrosothiol loss kinetics compared to the hydrophilic homopolymer analogue. Moreover, thiol-triggered degradation of the S-nitrosothiol was significantly slower when the S-nitrosothiol was embedded in a micellar structure. These results demonstrate that it is possible to incorporate nitric oxide donor moieties directly onto a polymer chain end, enabling simple synthesis of biochemically active nanostructures.

UR - http://pubs.acs.org/doi/pdf/10.1021/acsmacrolett.5b00733

U2 - 10.1021/acsmacrolett.5b00733

DO - 10.1021/acsmacrolett.5b00733

M3 - Article

VL - 4

SP - 1278

EP - 1282

JO - ACS Macro Letters

JF - ACS Macro Letters

SN - 2161-1653

IS - 11

ER -