Well-defined Poly(lactic Acid)s Containing Poly(ethylene Glycol) Side-chains

Overview

Journal Macromolecules

Date 2012 Jan 27

PMID 22279245

Citations 11

Authors

Jose A Castillo

Dorothee E Borchmann

Amy Y Cheng

Yufeng Wang

Chunhua Hu

Andres J Garcia

Marcus Weck

Affiliations

Soon will be listed here.

Abstract

Poly(ethylene glycol) (PEG) side-chain functionalized lactide analogues have been synthesized in four steps from commercially available L-lactide. The key step in the synthesis is the 1,3-dipolar cycloaddition between PEG-azides and a highly strained spirolactide-heptene monomer, which proceeds in high conversions. The PEG-grafted lactides analogues were polymerized via ring-opening polymerization using triazacyclodecene as organocatalyst to give well-defined tri- and hepta-(ethylene glycol)-poly(lactide)s (PLA) with molecular weights above 10 kDa and polydispersity indices between 1.6 and 2.1. PEG-poly(lactide) (PLA) with PEG chain M(n) 2000 was also prepared but GPC analysis showed a bimodal profile indicating the presence of starting macromonomer. Cell adhesion assays were performed using MC3T3 E-1 osteoblast-like cells demonstrating that PEG-containing PLA reduces cell adhesion significantly when compared to unfunctionalized PLA.

Citing Articles

Poly(Lactic Acid)-Based Graft Copolymers: Syntheses Strategies and Improvement of Properties for Biomedical and Environmentally Friendly Applications: A Review.

Coudane J, Van Den Berghe H, Mouton J, Garric X, Nottelet B Molecules. 2022; 27(13).

PMID: 35807380 PMC: 9268542. DOI: 10.3390/molecules27134135.

Novel Poly(Methylenelactide--L-Lactide) Graft Copolymers Synthesized by a Combination of Vinyl Addition and Ring-Opening Polymerizations.

Mekpothi T, Meepowpan P, Sriyai M, Molloy R, Punyodom W Polymers (Basel). 2021; 13(19).

PMID: 34641191 PMC: 8512580. DOI: 10.3390/polym13193374.

Synthesis of Precision Poly(1,3-adamantylene alkylene)s via Acyclic Diene Metathesis Polycondensation.

Friebel J, Ender C, Mezger M, Michels J, Wagner M, Wagener K Macromolecules. 2019; 52(12):4483-4491.

PMID: 31274929 PMC: 6595437. DOI: 10.1021/acs.macromol.9b00294.

Biodegradable zwitterionic sulfobetaine polymer and its conjugate with paclitaxel for sustained drug delivery.

Sun H, Chang M, Cheng W, Wang Q, Commisso A, Capeling M Acta Biomater. 2017; 64:290-300.

PMID: 29030301 PMC: 5682198. DOI: 10.1016/j.actbio.2017.10.016.

Solid Phase Stepwise Synthesis of Polyethylene Glycols.

Khanal A, Fang S Chemistry. 2017; 23(60):15133-15142.

PMID: 28834652 PMC: 5658237. DOI: 10.1002/chem.201703004.

References

Garcia A . Get a grip: integrins in cell-biomaterial interactions. Biomaterials. 2005; 26(36):7525-9. DOI: 10.1016/j.biomaterials.2005.05.029. View

Edlund U, Kallrot M, Albertsson A . Single-step covalent functionalization of polylactide surfaces. J Am Chem Soc. 2005; 127(24):8865-71. DOI: 10.1021/ja052073u. View

Dahl R, Finney N . A surprising dipolar cycloaddition provides ready access to aminoglycosides. J Am Chem Soc. 2004; 126(27):8356-7. DOI: 10.1021/ja0319238. View

Gopferich A, Peter S, Lucke A, Lu L, Mikos A . Modulation of marrow stromal cell function using poly(D,L-lactic acid)-block-poly(ethylene glycol)-monomethyl ether surfaces. J Biomed Mater Res. 1999; 46(3):390-8. DOI: 10.1002/(sici)1097-4636(19990905)46:3<390::aid-jbm12>3.0.co;2-n. View

Noga D, Petrie T, Kumar A, Weck M, Garcia A, Collard D . Synthesis and modification of functional poly(lactide) copolymers: toward biofunctional materials. Biomacromolecules. 2008; 9(7):2056-62. PMC: 7654554. DOI: 10.1021/bm800292z. View

Meier M, Schubert U . Evaluation of a new multiple-layer spotting technique for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry of synthetic polymers. Rapid Commun Mass Spectrom. 2003; 17(7):713-6. DOI: 10.1002/rcm.961. View

Becker J, Pounder R, Dove A . Synthesis of Poly(lactide)s with Modified Thermal and Mechanical Properties. Macromol Rapid Commun. 2011; 31(22):1923-37. DOI: 10.1002/marc.201000088. View

Hamamura K, Weng Y, Zhao J, Yokota H, Xie D . PEG attachment to osteoblasts enhances mechanosensitivity. Biomed Mater. 2008; 3(2):025017. DOI: 10.1088/1748-6041/3/2/025017. View

Pratt R, Lohmeijer B, Long D, Waymouth R, Hedrick J . Triazabicyclodecene: a simple bifunctional organocatalyst for acyl transfer and ring-opening polymerization of cyclic esters. J Am Chem Soc. 2006; 128(14):4556-7. DOI: 10.1021/ja060662+. View

10.

Heuberger M, Drobek T, Spencer N . Interaction forces and morphology of a protein-resistant poly(ethylene glycol) layer. Biophys J. 2004; 88(1):495-504. PMC: 1305026. DOI: 10.1529/biophysj.104.045443. View

11.

Jing F, Hillmyer M . A bifunctional monomer derived from lactide for toughening polylactide. J Am Chem Soc. 2008; 130(42):13826-7. DOI: 10.1021/ja804357u. View

12.

Gerhardt W, Noga D, Hardcastle K, Garcia A, Collard D, Weck M . Functional lactide monomers: methodology and polymerization. Biomacromolecules. 2006; 7(6):1735-42. PMC: 2535916. DOI: 10.1021/bm060024j. View

13.

Subramani K, Birch M . Fabrication of poly(ethylene glycol) hydrogel micropatterns with osteoinductive growth factors and evaluation of the effects on osteoblast activity and function. Biomed Mater. 2008; 1(3):144-54. DOI: 10.1088/1748-6041/1/3/009. View

14.

Iguerb O, Poleunis C, Mazeas F, Compere C, Bertrand P . Antifouling properties of poly(methyl methacrylate) films grafted with poly(ethylene glycol) monoacrylate immersed in seawater. Langmuir. 2008; 24(21):12272-81. DOI: 10.1021/la801814u. View

15.

Rubinshtein M, James C, Young J, Ma Y, Kobayashi Y, Gianneschi N . Facile procedure for generating side chain functionalized poly(alpha-hydroxy acid) copolymers from aldehydes via a versatile Passerini-type condensation. Org Lett. 2010; 12(15):3560-3. DOI: 10.1021/ol101433v. View

16.

Sant S, Nadeau V, Hildgen P . Effect of porosity on the release kinetics of propafenone-loaded PEG-g-PLA nanoparticles. J Control Release. 2005; 107(2):203-14. DOI: 10.1016/j.jconrel.2005.02.017. View