Novel poly(ethylene oxide monomethyl ether)-b-poly(ε-caprolactone) diblock copolymers containing a pH-acid labile ketal group as a block linkage
A new biocompatible and biodegradable diblock copolymer that contains a specific acid-labile degradable linkage (acyclic ketal group) between the hydrophobic poly(ε-caprolactone) (PCL) and the hydrophilic poly(ethylene oxide monomethyl ether) (MPEO) blocks is described herein. A multi-step synthetic...
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Veröffentlicht in: | Polymer chemistry 2014-01, Vol.5 (12), p.3884-3893 |
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creator | Petrova, S. Jäger, E. Konefał, R. Jäger, A. Venturini, C. G. Spěváček, J. Pavlova, E. Štěpánek, P. |
description | A new biocompatible and biodegradable diblock copolymer that contains a specific acid-labile degradable linkage (acyclic ketal group) between the hydrophobic poly(ε-caprolactone) (PCL) and the hydrophilic poly(ethylene oxide monomethyl ether) (MPEO) blocks is described herein. A multi-step synthetic method that combines carbodiimide chemistry, a “click” reaction and ring-opening polymerization (ROP) was employed to successfully produce a series of MPEO-
b
-PCL diblock copolymers (herein referred to as MPEO
44
-
b
-PCL
17
and MPEO
44
-
b
-PCL
44
). 2-{[2-(2-Azidoethoxy)propan-2-yl]}ethan-1-ol was obtained as a linker between the two blocks through a three-step synthetic approach. Furthermore, a newly developed α-methoxy-ω-hydroxy-poly(ethylene oxide) that contains an acid-labile ketal linkage was designed as a macroinitiator
via
a “click” reaction for the sequential controlled ring-opening polymerization of ε-CL. The newly obtained compounds (precursors, macromer, macroinitiator and final diblock copolymers) were assessed by
1
H NMR,
13
C NMR and FT-IR spectroscopy and SEC analysis, which are described in this manuscript. Upon dissolution in a mild organic solvent, the MPEO
44
-
b
-PCL
17
block copolymer self-assembled in water–PBS into regular, spherical, stable nanoparticles (NPs). Furthermore, the presence of the acid-labile ketal linker enabled the disassembly of these nanoparticles in a buffer that simulated acidic cytosolic or endosomal conditions in tumour cells as evaluated by dynamic light scattering (DLS), nanoparticle tracking analysis (NTA) and transmission electron microscopy (TEM) images. This disassembly led to hydrolysis profiles that resulted in neutral degradation products. |
doi_str_mv | 10.1039/C4PY00114A |
format | Article |
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b
-PCL diblock copolymers (herein referred to as MPEO
44
-
b
-PCL
17
and MPEO
44
-
b
-PCL
44
). 2-{[2-(2-Azidoethoxy)propan-2-yl]}ethan-1-ol was obtained as a linker between the two blocks through a three-step synthetic approach. Furthermore, a newly developed α-methoxy-ω-hydroxy-poly(ethylene oxide) that contains an acid-labile ketal linkage was designed as a macroinitiator
via
a “click” reaction for the sequential controlled ring-opening polymerization of ε-CL. The newly obtained compounds (precursors, macromer, macroinitiator and final diblock copolymers) were assessed by
1
H NMR,
13
C NMR and FT-IR spectroscopy and SEC analysis, which are described in this manuscript. Upon dissolution in a mild organic solvent, the MPEO
44
-
b
-PCL
17
block copolymer self-assembled in water–PBS into regular, spherical, stable nanoparticles (NPs). Furthermore, the presence of the acid-labile ketal linker enabled the disassembly of these nanoparticles in a buffer that simulated acidic cytosolic or endosomal conditions in tumour cells as evaluated by dynamic light scattering (DLS), nanoparticle tracking analysis (NTA) and transmission electron microscopy (TEM) images. This disassembly led to hydrolysis profiles that resulted in neutral degradation products.</description><identifier>ISSN: 1759-9954</identifier><identifier>EISSN: 1759-9962</identifier><identifier>DOI: 10.1039/C4PY00114A</identifier><language>eng</language><subject>Block copolymers ; Copolymers ; Degradation ; Disassembly ; Linkages ; Nanoparticles ; Oxides ; Polymerization</subject><ispartof>Polymer chemistry, 2014-01, Vol.5 (12), p.3884-3893</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c264t-d9eab1644743d92cc513a7d08e39051a2676ab293d7819f395caf67aa5df26f63</citedby><cites>FETCH-LOGICAL-c264t-d9eab1644743d92cc513a7d08e39051a2676ab293d7819f395caf67aa5df26f63</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,27903,27904</link.rule.ids></links><search><creatorcontrib>Petrova, S.</creatorcontrib><creatorcontrib>Jäger, E.</creatorcontrib><creatorcontrib>Konefał, R.</creatorcontrib><creatorcontrib>Jäger, A.</creatorcontrib><creatorcontrib>Venturini, C. G.</creatorcontrib><creatorcontrib>Spěváček, J.</creatorcontrib><creatorcontrib>Pavlova, E.</creatorcontrib><creatorcontrib>Štěpánek, P.</creatorcontrib><title>Novel poly(ethylene oxide monomethyl ether)-b-poly(ε-caprolactone) diblock copolymers containing a pH-acid labile ketal group as a block linkage</title><title>Polymer chemistry</title><description>A new biocompatible and biodegradable diblock copolymer that contains a specific acid-labile degradable linkage (acyclic ketal group) between the hydrophobic poly(ε-caprolactone) (PCL) and the hydrophilic poly(ethylene oxide monomethyl ether) (MPEO) blocks is described herein. A multi-step synthetic method that combines carbodiimide chemistry, a “click” reaction and ring-opening polymerization (ROP) was employed to successfully produce a series of MPEO-
b
-PCL diblock copolymers (herein referred to as MPEO
44
-
b
-PCL
17
and MPEO
44
-
b
-PCL
44
). 2-{[2-(2-Azidoethoxy)propan-2-yl]}ethan-1-ol was obtained as a linker between the two blocks through a three-step synthetic approach. Furthermore, a newly developed α-methoxy-ω-hydroxy-poly(ethylene oxide) that contains an acid-labile ketal linkage was designed as a macroinitiator
via
a “click” reaction for the sequential controlled ring-opening polymerization of ε-CL. The newly obtained compounds (precursors, macromer, macroinitiator and final diblock copolymers) were assessed by
1
H NMR,
13
C NMR and FT-IR spectroscopy and SEC analysis, which are described in this manuscript. Upon dissolution in a mild organic solvent, the MPEO
44
-
b
-PCL
17
block copolymer self-assembled in water–PBS into regular, spherical, stable nanoparticles (NPs). Furthermore, the presence of the acid-labile ketal linker enabled the disassembly of these nanoparticles in a buffer that simulated acidic cytosolic or endosomal conditions in tumour cells as evaluated by dynamic light scattering (DLS), nanoparticle tracking analysis (NTA) and transmission electron microscopy (TEM) images. This disassembly led to hydrolysis profiles that resulted in neutral degradation products.</description><subject>Block copolymers</subject><subject>Copolymers</subject><subject>Degradation</subject><subject>Disassembly</subject><subject>Linkages</subject><subject>Nanoparticles</subject><subject>Oxides</subject><subject>Polymerization</subject><issn>1759-9954</issn><issn>1759-9962</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2014</creationdate><recordtype>article</recordtype><recordid>eNpFUEFOwzAQjBBIVNALL_CxRQrYcWzXx6oCilQBBzhwijbOppg6cYhTRJ_BY_gGbyJtEexhd7Qzs9JOFJ0xesEo15ez9OGZUsbS6UE0YEroWGuZHP5hkR5HwxBeaV-cpQmXg-jzzr-jI413mxF2LxuHNRL_YQskla99tduRvmM7jvN4p_v-ig00rXdgOl_jmBQ2d96siPFbvsI29LDuwNa2XhIgzTwGYwviILcOyQo7cGTZ-nVDIPT83u1svYIlnkZHJbiAw995Ej1dXz3O5vHi_uZ2Nl3EJpFpFxcaIWcyTVXKC50YIxgHVdAJck0Fg0QqCXmieaEmTJdcCwOlVACiKBNZSn4SjfZ3-0_e1hi6rLLBoHNQo1-HjAnBqJoomvTS873UtD6EFsusaW0F7SZjNNtGn_1Hz38ANrV4wA</recordid><startdate>20140101</startdate><enddate>20140101</enddate><creator>Petrova, S.</creator><creator>Jäger, E.</creator><creator>Konefał, R.</creator><creator>Jäger, A.</creator><creator>Venturini, C. G.</creator><creator>Spěváček, J.</creator><creator>Pavlova, E.</creator><creator>Štěpánek, P.</creator><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8FD</scope><scope>JG9</scope></search><sort><creationdate>20140101</creationdate><title>Novel poly(ethylene oxide monomethyl ether)-b-poly(ε-caprolactone) diblock copolymers containing a pH-acid labile ketal group as a block linkage</title><author>Petrova, S. ; Jäger, E. ; Konefał, R. ; Jäger, A. ; Venturini, C. G. ; Spěváček, J. ; Pavlova, E. ; Štěpánek, P.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c264t-d9eab1644743d92cc513a7d08e39051a2676ab293d7819f395caf67aa5df26f63</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2014</creationdate><topic>Block copolymers</topic><topic>Copolymers</topic><topic>Degradation</topic><topic>Disassembly</topic><topic>Linkages</topic><topic>Nanoparticles</topic><topic>Oxides</topic><topic>Polymerization</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Petrova, S.</creatorcontrib><creatorcontrib>Jäger, E.</creatorcontrib><creatorcontrib>Konefał, R.</creatorcontrib><creatorcontrib>Jäger, A.</creatorcontrib><creatorcontrib>Venturini, C. G.</creatorcontrib><creatorcontrib>Spěváček, J.</creatorcontrib><creatorcontrib>Pavlova, E.</creatorcontrib><creatorcontrib>Štěpánek, P.</creatorcontrib><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><jtitle>Polymer chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Petrova, S.</au><au>Jäger, E.</au><au>Konefał, R.</au><au>Jäger, A.</au><au>Venturini, C. G.</au><au>Spěváček, J.</au><au>Pavlova, E.</au><au>Štěpánek, P.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Novel poly(ethylene oxide monomethyl ether)-b-poly(ε-caprolactone) diblock copolymers containing a pH-acid labile ketal group as a block linkage</atitle><jtitle>Polymer chemistry</jtitle><date>2014-01-01</date><risdate>2014</risdate><volume>5</volume><issue>12</issue><spage>3884</spage><epage>3893</epage><pages>3884-3893</pages><issn>1759-9954</issn><eissn>1759-9962</eissn><abstract>A new biocompatible and biodegradable diblock copolymer that contains a specific acid-labile degradable linkage (acyclic ketal group) between the hydrophobic poly(ε-caprolactone) (PCL) and the hydrophilic poly(ethylene oxide monomethyl ether) (MPEO) blocks is described herein. A multi-step synthetic method that combines carbodiimide chemistry, a “click” reaction and ring-opening polymerization (ROP) was employed to successfully produce a series of MPEO-
b
-PCL diblock copolymers (herein referred to as MPEO
44
-
b
-PCL
17
and MPEO
44
-
b
-PCL
44
). 2-{[2-(2-Azidoethoxy)propan-2-yl]}ethan-1-ol was obtained as a linker between the two blocks through a three-step synthetic approach. Furthermore, a newly developed α-methoxy-ω-hydroxy-poly(ethylene oxide) that contains an acid-labile ketal linkage was designed as a macroinitiator
via
a “click” reaction for the sequential controlled ring-opening polymerization of ε-CL. The newly obtained compounds (precursors, macromer, macroinitiator and final diblock copolymers) were assessed by
1
H NMR,
13
C NMR and FT-IR spectroscopy and SEC analysis, which are described in this manuscript. Upon dissolution in a mild organic solvent, the MPEO
44
-
b
-PCL
17
block copolymer self-assembled in water–PBS into regular, spherical, stable nanoparticles (NPs). Furthermore, the presence of the acid-labile ketal linker enabled the disassembly of these nanoparticles in a buffer that simulated acidic cytosolic or endosomal conditions in tumour cells as evaluated by dynamic light scattering (DLS), nanoparticle tracking analysis (NTA) and transmission electron microscopy (TEM) images. This disassembly led to hydrolysis profiles that resulted in neutral degradation products.</abstract><doi>10.1039/C4PY00114A</doi><tpages>10</tpages></addata></record> |
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source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
subjects | Block copolymers Copolymers Degradation Disassembly Linkages Nanoparticles Oxides Polymerization |
title | Novel poly(ethylene oxide monomethyl ether)-b-poly(ε-caprolactone) diblock copolymers containing a pH-acid labile ketal group as a block linkage |
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