Copolymacrolactones Grafted with <span style="font-variant: small-caps">l</span>-Glutamic Acid: Synthesis, Structure, and Nanocarrier Properties
The enzymatic ring-opening copolymerization (eROP) of globalide (Gl) and pentadecalactone (PDL) was performed in solution from mixtures of the two macrolactones at ratios covering the whole range of comonomeric compositions. The resulting P(Gl<sub>x</sub>-<i>r</i>-PDL<sub&...
| Main Authors: | , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2020-04-01
|
| Series: | Polymers |
| Subjects: | |
| Online Access: | https://www.mdpi.com/2073-4360/12/4/995 |
| _version_ | 1797569667410165760 |
|---|---|
| author | Ernesto Tinajero-Díaz Antxon Martínez de Ilarduya Sebastián Muñoz-Guerra |
| author_facet | Ernesto Tinajero-Díaz Antxon Martínez de Ilarduya Sebastián Muñoz-Guerra |
| author_sort | Ernesto Tinajero-Díaz |
| collection | DOAJ |
| description | The enzymatic ring-opening copolymerization (eROP) of globalide (Gl) and pentadecalactone (PDL) was performed in solution from mixtures of the two macrolactones at ratios covering the whole range of comonomeric compositions. The resulting P(Gl<sub>x</sub>-<i>r</i>-PDL<sub>y</sub>) random copolyesters were aminofunctionalized by thiol-ene reaction with aminoethanethiol. ROP of γ-benzyl-<span style="font-variant: small-caps;">l</span>-glutamate <i>N</i>-carboxyanhydride initiated by P(Gl<sub>x</sub>-<i>r</i>-PDL<sub>y</sub>)-NH<sub>2</sub> provided neutral poly(γ-benzyl-<span style="font-variant: small-caps;">l</span>-glutamate)-grafted copolyesters, which were converted by hydrolysis into negatively charged hybrid copolymers. Both water-soluble and nonsoluble copolymers were produced depending on copolymer charge and their grafting degree, and their capacity for self-assembling in nano-objects were comparatively examined. The emulsion solvent-evaporation technique applied to the chloroform-soluble copolymers grafted with benzyl glutamate rendered well-delineated spherical nanoparticles with an average diameter of 200–300 nm. Conversely, micellar solutions in water were produced from copolyesters bearing grafted chains composed of at least 10 units of glutamic acid in the free form. The copolymer micelles were shown to be able to load doxorubicin (DOX) efficiently through electrostatic interactions and also to release the drug at a rate that was markedly pH dependent. |
| first_indexed | 2024-03-10T20:14:49Z |
| format | Article |
| id | doaj.art-ca8b52f5736a414280b6664a863badc8 |
| institution | Directory Open Access Journal |
| issn | 2073-4360 |
| language | English |
| last_indexed | 2024-03-10T20:14:49Z |
| publishDate | 2020-04-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Polymers |
| spelling | doaj.art-ca8b52f5736a414280b6664a863badc82023-11-19T22:40:01ZengMDPI AGPolymers2073-43602020-04-0112499510.3390/polym12040995Copolymacrolactones Grafted with <span style="font-variant: small-caps">l</span>-Glutamic Acid: Synthesis, Structure, and Nanocarrier PropertiesErnesto Tinajero-Díaz0Antxon Martínez de Ilarduya1Sebastián Muñoz-Guerra2Departament d´Enginyeria Química, Universitat Politècnica de Catalunya, ETSEIB, Diagonal 647, 08028 Barcelona, SpainDepartament d´Enginyeria Química, Universitat Politècnica de Catalunya, ETSEIB, Diagonal 647, 08028 Barcelona, SpainDepartament d´Enginyeria Química, Universitat Politècnica de Catalunya, ETSEIB, Diagonal 647, 08028 Barcelona, SpainThe enzymatic ring-opening copolymerization (eROP) of globalide (Gl) and pentadecalactone (PDL) was performed in solution from mixtures of the two macrolactones at ratios covering the whole range of comonomeric compositions. The resulting P(Gl<sub>x</sub>-<i>r</i>-PDL<sub>y</sub>) random copolyesters were aminofunctionalized by thiol-ene reaction with aminoethanethiol. ROP of γ-benzyl-<span style="font-variant: small-caps;">l</span>-glutamate <i>N</i>-carboxyanhydride initiated by P(Gl<sub>x</sub>-<i>r</i>-PDL<sub>y</sub>)-NH<sub>2</sub> provided neutral poly(γ-benzyl-<span style="font-variant: small-caps;">l</span>-glutamate)-grafted copolyesters, which were converted by hydrolysis into negatively charged hybrid copolymers. Both water-soluble and nonsoluble copolymers were produced depending on copolymer charge and their grafting degree, and their capacity for self-assembling in nano-objects were comparatively examined. The emulsion solvent-evaporation technique applied to the chloroform-soluble copolymers grafted with benzyl glutamate rendered well-delineated spherical nanoparticles with an average diameter of 200–300 nm. Conversely, micellar solutions in water were produced from copolyesters bearing grafted chains composed of at least 10 units of glutamic acid in the free form. The copolymer micelles were shown to be able to load doxorubicin (DOX) efficiently through electrostatic interactions and also to release the drug at a rate that was markedly pH dependent.https://www.mdpi.com/2073-4360/12/4/995macrolactones ROPpentadecanolactone ROPglobalide ROPmacrolactones copolyesterspolyester-polypeptide graft copolymerspolyglutamic grafted polyesters |
| spellingShingle | Ernesto Tinajero-Díaz Antxon Martínez de Ilarduya Sebastián Muñoz-Guerra Copolymacrolactones Grafted with <span style="font-variant: small-caps">l</span>-Glutamic Acid: Synthesis, Structure, and Nanocarrier Properties Polymers macrolactones ROP pentadecanolactone ROP globalide ROP macrolactones copolyesters polyester-polypeptide graft copolymers polyglutamic grafted polyesters |
| title | Copolymacrolactones Grafted with <span style="font-variant: small-caps">l</span>-Glutamic Acid: Synthesis, Structure, and Nanocarrier Properties |
| title_full | Copolymacrolactones Grafted with <span style="font-variant: small-caps">l</span>-Glutamic Acid: Synthesis, Structure, and Nanocarrier Properties |
| title_fullStr | Copolymacrolactones Grafted with <span style="font-variant: small-caps">l</span>-Glutamic Acid: Synthesis, Structure, and Nanocarrier Properties |
| title_full_unstemmed | Copolymacrolactones Grafted with <span style="font-variant: small-caps">l</span>-Glutamic Acid: Synthesis, Structure, and Nanocarrier Properties |
| title_short | Copolymacrolactones Grafted with <span style="font-variant: small-caps">l</span>-Glutamic Acid: Synthesis, Structure, and Nanocarrier Properties |
| title_sort | copolymacrolactones grafted with span style font variant small caps l span glutamic acid synthesis structure and nanocarrier properties |
| topic | macrolactones ROP pentadecanolactone ROP globalide ROP macrolactones copolyesters polyester-polypeptide graft copolymers polyglutamic grafted polyesters |
| url | https://www.mdpi.com/2073-4360/12/4/995 |
| work_keys_str_mv | AT ernestotinajerodiaz copolymacrolactonesgraftedwithspanstylefontvariantsmallcapslspanglutamicacidsynthesisstructureandnanocarrierproperties AT antxonmartinezdeilarduya copolymacrolactonesgraftedwithspanstylefontvariantsmallcapslspanglutamicacidsynthesisstructureandnanocarrierproperties AT sebastianmunozguerra copolymacrolactonesgraftedwithspanstylefontvariantsmallcapslspanglutamicacidsynthesisstructureandnanocarrierproperties |