Star-Shaped Copolymers Based on Poly(N-vinylcaprolactam) and their Use as Nanocarriers of Methotrexate
Norma A. Cortez-Lemus A B and Angel Licea-Claverie AA Centro de Graduados e Investigación en Química, Instituto Tecnológico de Tijuana, Apartado Postal 1166, Tijuana, Baja California 22000, México.
B Corresponding author. Email: ncortez@tectijuana.mx
Australian Journal of Chemistry 70(12) 1291-1301 https://doi.org/10.1071/CH17325
Submitted: 13 June 2017 Accepted: 7 July 2017 Published: 8 August 2017
Abstract
Star-shaped poly(N-vinylcaprolactam)-block-poly(ethylhexylacrylate)-block-polyethylene glycol (PNVCL-b-PEHA-b-PEG) triblock copolymers and star-shaped poly(N-vinylcaprolactam)-block-polyethylene glycol (PNVCL-b-PEG) diblock copolymers were synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization. The resulting star block copolymers were characterized using 1H NMR and UV-vis spectroscopy, gel permeation chromatography, and dynamic light scattering. The star-shaped PNVCL-b-PEG and PNVCL-b-PEHA-b-PEG block copolymers self-assemble spontaneously into aggregates in water. The aggregates formed ranged from ~17 to 135 nm in diameter and were used to encapsulate methotrexate (MTX). It was observed that the aggregates from PNVCL-b-PEHA-b-PEG copolymers exhibited a higher drug loading and a lower release of MTX (19 wt-% and 54 %) as compared with star copolymers without PEHA (5 wt-% and 81 %) after 24 h at a temperature below their lower critical solution temperature values.
References
[1] Y. Zhang, H. F. Chan, K. W. Leong, Adv. Drug Deliv. Rev. 2013, 65, 104.| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38Xhs1ajsLbN&md5=635f8df9ec3aa64d888cd7f8203016c9CAS |
[2] N. Nishiyama, Y. Matsumura, K. Kataoka, Cancer Sci. 2016, 107, 867.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC28XhtVCis7vK&md5=a68661b9c25505cc840b8179e22650d0CAS |
[3] C. Xie, P. Zhang, Z. Zhang, C. Yang, J. Zhang, W. Wu, X. Jiang, Nanoscale 2015, 7, 12572.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2MXhtVSgsbbM&md5=ebc387b4347790010816030ecaa36f03CAS |
[4] G. Gaucher, K. Asahina, J. Wang, J.-C. Leroux, Biomacromolecules 2009, 10, 408.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXktVykug%3D%3D&md5=02c75014c68ae43aaf9210def199f37fCAS |
[5] K. Knop, R. Hoogenboom, D. Fischer, U. S. Schubert, Angew. Chem. Int. Ed. 2010, 49, 6288.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXhtVOqtLbN&md5=1d2267e7ec0327764b6249082eb09cf1CAS |
[6] R. B. Greenwald, Y. H. Choe, J. McGuire, C. D. Conover, Adv. Drug Deliv. Rev. 2003, 55, 217.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXmsVGiuw%3D%3D&md5=45f6c9947af9a2650f1cc1e71e263956CAS |
[7] S. A. Senevirathne, K. E. Washington, M. C. Biewer, M. C. Stefan, J. Mater. Chem. 2016, 4, 360.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2MXhvF2hsrvN&md5=a423c3617c87114cde1784f18bf48a0cCAS |
[8] P. Mishra, B. Nayak, R. K. Dey, Asian J. Pharm. Sci. 2016, 11, 337.
| Crossref | GoogleScholarGoogle Scholar |
[9] K. S. Lee, H. C. Chung, S. A. Im, Y. H. Park, C. S. Kim, S.-B. Kim, S. Y. Rha, M. Y. Lee, J. Ro, Breast Cancer Res. Treat. 2008, 108, 241.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXitleqsbY%3D&md5=10f73c11379c614d3dd2c8c023882d48CAS |
[10] Y. Zhang, T. Jin, R. Zhuo, Colloid. Surf. B. 2005, 44, 104.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2MXntVCqur0%3D&md5=faced67755a594b3d9071543283c7dffCAS |
[11] W.-Q. Chen, H. Wei, S. L. Li, J. Feng, J. Nie, X.-Z. Zhang, R.-X. Zhuo, Polymer 2008, 49, 3965.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXpvVKmtrw%3D&md5=d55f4123fccd93e2be59d7e4b0770929CAS |
[12] S. K. Hira, K. Ramesh, U. Gupta, K. Mitra, N. Misra, B. Ray, P. P. Manna, ACS Appl. Mater. Interfaces 2015, 7, 20021.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2MXhtlymsLzL&md5=492cf289031613241ba89f85dad46580CAS |
[13] W. Wu, W. Wang, J. Li, Prog. Polym. Sci. 2015, 46, 55.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2MXjtFCjsbY%3D&md5=7580bc0684fa0b137d1d548495e0dbd7CAS |
[14] J. M. Ren, T. G. McKenzie, Q. Fu, E. H. Wong, J. Xu, Z. An, S. Shanmugam, T. P. Davis, C. Boyer, G. G. Qiao, Chem. Rev. 2016, 116, 6743.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC28XpsFOhsrw%3D&md5=d7153d926879f76418fb7072ba4ccb8bCAS |
[15] G. D. García-Olaiz, K. A. Montoya-Villegas, A. Licea-Claverie, N. A. Cortez-Lemus, React. Funct. Polym. 2015, 88, 16.
| Crossref | GoogleScholarGoogle Scholar |
[16] N. A. Cortez-Lemus, A. Licea-Claverie, Prog. Polym. Sci. 2016, 53, 1.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2MXhtlOmtrrO&md5=3a735550d862b4222c7e83808aad25b3CAS |
[17] N. A. Cortez-Lemus, A. Licea-Claverie, J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 2156.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC28XktlGntb4%3D&md5=34dab46d4132e492a601673850af4c4bCAS |
[18] J. Rieger, F. Stoffelbach, C. Bui, D. Alaimo, C. Jérôme, B. Charleux, Macromolecules 2008, 41, 4065.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXmtF2rt78%3D&md5=7e23802c72da3bd71b440a0fe9862635CAS |
[19] T. Boursier, I. Chaduc, J. Rieger, F. D’Agosto, M. Lansalot, B. Charleux, Polym. Chem. 2011, 2, 355.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXitVyiu7s%3D&md5=47cfbac2310dcb2633f7b7ee1e8cb09dCAS |
[20] J. W. Bartels, S. I. Cauët, P. L. Billings, L. Y. Lin, J. H. Zhu, C. Fidge, D. J. Pochan, K. L. Wooley, Macromolecules 2010, 43, 7128.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXpvVGgsbY%3D&md5=de67c6aab832fa9307a7f0991902370bCAS |
[21] N. J. Warren, O. O. Mykhaylyk, D. Mahmood, A. J. Ryan, S. P. Armes, J. Am. Chem. Soc. 2014, 136, 1023.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3sXhvFKqt7fF&md5=c1aadca3f9a6dd2254c3ef2c13d6c47aCAS |
[22] H. Y. Cho, S. E. Averick, E. Paredes, K. Wegner, A. Averick, S. Jurga, S. R. Das, K. Matyjaszewski, Biomacromolecules 2013, 14, 1262.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3sXlsVeru7w%3D&md5=198ed402eb8e2017006423b1d73bcfa1CAS |
[23] H. Gao, K. Matyjaszewski, J. Am. Chem. Soc. 2007, 129, 11828.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXpvVCntLY%3D&md5=e734deb835bc4485107e1bb89399813aCAS |
