Abstract
H2S-releasing polymers with an acyl-protected perthiol chain terminus were prepared using a simple, high yielding end-group modification process. Specifically, benzodithioate-terminated poly(oligoethylene glycol methyl ether) methacrylate (POEGMA) was first converted to pyridyl-2-disulfide-terminated polymer, after which a thiol-disulfide exchange reaction with thiobenzoic acid yielded an acyl protected perthiol at the chain terminus. The same approach was successfully applied to a hydrophilic-hydrophobic block polymer, P[OEGMA-block-n-butyl methacrylate], and a pH-responsive block copolymer, P[OEGMA-co-N,N-(dimethylamino) ethyl methacrylate-block-N,N-(diisopropylamino)ethyl methacrylate]. All polymers were shown to release H2S when exposed to thiol (l-cysteine), with release rate dependent on polymer structure. In the case of the pH-responsive block copolymer there was minimal release of H2S under conditions where the polymers were micellised, whereas there was rapid, sustained release when the block copolymers were in unimeric form. These materials were shown to increase the intracellular concentration of H2S when applied to HEK cells, and may be useful for interrogating localized delivery of H2S.
| Original language | English |
|---|---|
| Pages (from-to) | 6362-6367 |
| Number of pages | 6 |
| Journal | Polymer Chemistry |
| Volume | 8 |
| Issue number | 41 |
| DOIs | |
| Publication status | Published - 7 Nov 2017 |
Cite this
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Polymers with acyl-protected perthiol chain termini as convenient building blocks for doubly responsive H2S-donating nanoparticles. / Yu, Sul Hwa; Ercole, Francesca; Veldhuis, Nicholas A.; Whittaker, Michael R.; Davis, Thomas P.; Quinn, John F.
In: Polymer Chemistry, Vol. 8, No. 41, 07.11.2017, p. 6362-6367.Research output: Contribution to journal › Article › Research › peer-review
TY - JOUR
T1 - Polymers with acyl-protected perthiol chain termini as convenient building blocks for doubly responsive H2S-donating nanoparticles
AU - Yu, Sul Hwa
AU - Ercole, Francesca
AU - Veldhuis, Nicholas A.
AU - Whittaker, Michael R.
AU - Davis, Thomas P.
AU - Quinn, John F.
PY - 2017/11/7
Y1 - 2017/11/7
N2 - H2S-releasing polymers with an acyl-protected perthiol chain terminus were prepared using a simple, high yielding end-group modification process. Specifically, benzodithioate-terminated poly(oligoethylene glycol methyl ether) methacrylate (POEGMA) was first converted to pyridyl-2-disulfide-terminated polymer, after which a thiol-disulfide exchange reaction with thiobenzoic acid yielded an acyl protected perthiol at the chain terminus. The same approach was successfully applied to a hydrophilic-hydrophobic block polymer, P[OEGMA-block-n-butyl methacrylate], and a pH-responsive block copolymer, P[OEGMA-co-N,N-(dimethylamino) ethyl methacrylate-block-N,N-(diisopropylamino)ethyl methacrylate]. All polymers were shown to release H2S when exposed to thiol (l-cysteine), with release rate dependent on polymer structure. In the case of the pH-responsive block copolymer there was minimal release of H2S under conditions where the polymers were micellised, whereas there was rapid, sustained release when the block copolymers were in unimeric form. These materials were shown to increase the intracellular concentration of H2S when applied to HEK cells, and may be useful for interrogating localized delivery of H2S.
AB - H2S-releasing polymers with an acyl-protected perthiol chain terminus were prepared using a simple, high yielding end-group modification process. Specifically, benzodithioate-terminated poly(oligoethylene glycol methyl ether) methacrylate (POEGMA) was first converted to pyridyl-2-disulfide-terminated polymer, after which a thiol-disulfide exchange reaction with thiobenzoic acid yielded an acyl protected perthiol at the chain terminus. The same approach was successfully applied to a hydrophilic-hydrophobic block polymer, P[OEGMA-block-n-butyl methacrylate], and a pH-responsive block copolymer, P[OEGMA-co-N,N-(dimethylamino) ethyl methacrylate-block-N,N-(diisopropylamino)ethyl methacrylate]. All polymers were shown to release H2S when exposed to thiol (l-cysteine), with release rate dependent on polymer structure. In the case of the pH-responsive block copolymer there was minimal release of H2S under conditions where the polymers were micellised, whereas there was rapid, sustained release when the block copolymers were in unimeric form. These materials were shown to increase the intracellular concentration of H2S when applied to HEK cells, and may be useful for interrogating localized delivery of H2S.
UR - http://www.scopus.com/inward/record.url?scp=85032456058&partnerID=8YFLogxK
U2 - 10.1039/c7py01484h
DO - 10.1039/c7py01484h
M3 - Article
VL - 8
SP - 6362
EP - 6367
JO - Polymer Chemistry
JF - Polymer Chemistry
SN - 1759-9954
IS - 41
ER -