Amphiphilic copolymers of ε-caprolactone and γ-substituted ε-caprolactone. Synthesis and functionalization of poly(D,L-lactide) nanoparticles
Open accessAbstract
Fully biodegradable and surface-functionalized poly(D,L-lactide) (PLA) nanoparticles have been prepared by a co-precipitation technique. Novel amphiphilic random copolyesters P(CL-co-gammaXCL) were synthesized by controlled copolymerization of epsilon-caprolactone and epsilon-caprolactone substituted in the gamma-position by a hydrophilic X group, where X is either a cationic pyridinium (gammaPyCL) or a non-ionic hydroxyl (gammaOHCL). Nanoparticles were prepared by co-precipitation of PLA with the P(CL-co-gammaXCL) copolyester from a DMSO solution. Small amounts of cationic P(CL-co-gammaPyCL) copolymers are needed to quantitatively form stable nanoparticles (ca. 10 mg/ 100 mg PLA), although larger amounts of non-ionic P(CL-co-gammaOHCL) copolymers are needed (> or = 12.5 mg/ 100 mg PLA). Copolymers with a low degree of polymerization (ca. 40) are more efficient stabilizers, probably because of faster migration towards the nanoparticle-water interface. The nanoparticle diameter decreases with the polymer concentration in DMSO, e.g. from ca. 160 nm (16 mg/ml) to ca. 100 nm (2 mg/ml) for PLA/P(CL-co-gammaPyCL) nanoparticles. Migration of the P(CL-co-gammaXCL) copolyesters to the nanoparticle surface was confirmed by measurement of the zeta potential, i.e. ca. +65 mV for P(CL-co-gammaPCL) and -7 mV for P(CL-co-gammaOHCL). The polyamphiphilic copolyesters stabilize PLA nanoparticles by electrostatic or steric repulsions, depending on whether they are charged or not. They also impart functionality and reactivity to the surface, which opens up new opportunities for labelling and targeting purposes.
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PCL containing more than 50 mol% of γ-triethylsilanolate could not be quantitatively converted into hydroxyl containing PCL without degradation.
“For instance, PCL containing more than 50 mol% of γ-triethylsilanolate (-OSiEt 3 ) could not be quantitatively converted into hydroxyl containing PCL without degradation [106].”
From Recent advances in the synthesis of aliphatic polyesters by ring-opening polymerization☆ (2008) · cites this paper as [106]
A series of lactones substituted by bromides, acrylates, protected hydroxyl groups, protected carboxyl groups, and terminal olefins or containing ketones have been synthesized and homo- or co-polymerized.
“Later on, a series of lactones substituted by bromides [103,104], acrylates [105], protected hydroxyl goups [106,107] protected carboxyl groups [108][109][110][111][112][113][114][115] and terminal olefins [116,117] or containing ketones [118] have been synthesized and homo-or co-polymerized.”
From Recent advances in the synthesis of aliphatic polyesters by ring-opening polymerization☆ (2008) · cites this paper as [106]
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- Authors
- Gautier, S., D'Aloia, V., Halleux, O., Mazza, M., Lecomte, P., & Jérôme, R.
- Affiliations
- University of Liège (BE)
- Venue
- Journal of Biomaterials Science, Polymer Edition
- Publisher
- Informa UK Limited
- Published
- 2003-01
- Volume
- 14
- Issue
- 1
- Pages
- 63-85
- ISSN
- 0920-5063 (ISSN-L)
- 1568-5624
- OpenAlex
- W1990528638
- Cited by
- 49
- References
- 26
- Citations by year
- 2026: 1 · 2025: 3 · 2024: 1 · 2023: 1 · 2022: 1 · 2020: 2 · 2019: 2 · 2018: 1 · 2017: 1 · 2016: 1 · 2015: 1 · 2014: 2 · 2013: 1 · 2012: 3
- FWCI
- 1.42
- Type
- journal article
- Language
- en
- Open access
- green
- orbi.uliege.be
- Licence
- other-oa
- Locations
- Journal of Biomaterials Science Polymer Edition (publishedVersion)
- PubMed (publishedVersion)
- ORBi (University of Liège) (submittedVersion, other-oa)
- Funders
- Services Fédéraux des Affaires Scientifiques, Techniques et Culturelles
- Topics
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Materials Science › Biomaterials › Nanoparticle-Based Drug Delivery
- Physical Sciences › Materials Science › Materials Chemistry › Pickering emulsions and particle stabilization
- Keywords
- ε-caprolactone, co-precipitation, nanoparticle stabilization, surface functionalization, zeta potential, electrostatic repulsion, steric repulsion, biodegradable polymers
- MeSH terms
- Biodegradation, Environmental, Excipients, Particle Size, Polyesters, Surface-Active Agents, Nanotechnology
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