Synthesis of P4VP-b-PBLG Diblock Copolymers and Their Self-Assembly Behavior
- 1 School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, China
- 2 School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, China
- 3 School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, China
Abstract
Well-defined P4VP-b-PBLG diblock polymer composed of poly (4-vinylpyridine) (P4VP) and poly ( γ -benzyl-L-glutamate) (PBLG) was synthesized by click reaction with alkyne- and azide-functionalized homopolymers. Besides, P4VP blocks were synthesized by copper-mediated atom transfer radical polymerization (ATRP) with a chlorine-containing alkyne bifunctional initiator, and the azido-terminated PBLG homopolymers were synthesized by ring-opening polymerization (ROP) of γ -benzyl-L-glutamate with an amine-containing azide initiator. In addition, the synthesized P4VP-b-PBLG with different block ratios has been characterized by proton nuclear magnetic resonance ( 1 H NMR), Gel permeation chromatograph (GPC) and fourier transform infrated spectroscopy (FT-IR). Then, the self-assembly behaviors of P4VP-b-PBLG have been studied by changing parameters like dripping speed and block ratio. The morphologies of self-assembly of spherical, disk-like and ellipsoid-like shape particles have been observed and analyzed by scanning electron microscopy (SEM). These results have provided guidelines for the design of macromolecular self-assembly.
- Rhodes, A.J. and Deming, T.J. (2013) Soluble, Clickable Polypeptides from Azide-Containing N-Carboxyanhydride Monomers. ACS Macro Letters, 2, 351-354. https://doi.org/10.1021/mz4001089
- Tang, H.Y. and Zhang, D.H. (2011) Multi-Functionalization of Helical Block Copoly(α-Peptide)s by Orthogonal Chemistry. Polymer Chemistry, 2, 1542-1551. https://doi.org/10.1039/c1py00015b
- Rapoport, N. (2007) Physical Stimuli-Responsive Polymeric Micelles for Anti-Cancer Drug Delivery. Progress in Polymer Science, 32, 962-990. https://doi.org/10.1016/j.progpolymsci.2007.05.009
- Knoop, R.J.I., de Geus, M., Habraken, G.J.M., Koning, C.E., Menzel, H. and Heise, A. (2010) Stimuli Responsive Peptide Conjugated Polymer Nanoparticles. Macromolecules, 43, 4126-4132. https://doi.org/10.1021/ma100327p
- Shim, M.S. and Kwon, Y.J. (2010) Acid-Transforming Polypeptide Micelles for Targeted Nonviral Gene Delivery. Biomaterials, 31, 3404-3413. https://doi.org/10.1016/j.biomaterials.2010.01.019
- Zhang, A., Li, J.G., Wang, T., Wu, D.L., Zhang, X.Q., Yan, J.T., Du, S., Guo, Y.F. and Wang, J.T. (2008) Stimuli-Responsive Zwitterionic Block Copolypeptides: Poly(N-Isopropylacrylamide)-Block-Poly(Lysine-Co-Glutamic Acid). Biomacromolecules, 9, 2670-2676. https://doi.org/10.1021/bm800394p
- Israelachvili, J.N. (2011) Intermolecular and Surface Forces. Soft Matter, 7, 4122-4138.
- Checot, F., Rodrıguez-Hernandez, J., Gnanou, Y. and Lecommandoux, S. (2006) Responsive Micelles and Vesicles Based on Polypeptide Diblock Copolymers. Polymers for Advanced Technologies, 17, 782-785. https://doi.org/10.1002/pat.821
- Chécot, F., Brûlet, A., Oberdisse, J., Gnanou, Y.O., Mondain-Monval, S. and Lecommandoux, S. (2005) Structure of Polypeptide-Based Diblock Copolymers in Solution: Stimuli-Responsive Vesicles and Micelles. Langmuir, 21, 4308-4315. https://doi.org/10.1021/la0468500
- Lee, M., Cho, B.-K. and Zin, W.-C. (2001) Supramolecular Structures from Rod-Coil Block Copolymers. Chemical Reviews, 101, 3869-3892. https://doi.org/10.1021/cr0001131
- Kim, K.T., Park, C., Vandermeulen, G.W.M., Rider, D.A., Kim, C., Winnik, M.A. and Manners, I. (2005) Gelation of Helical Polypeptide-Random Coil Diblock Copolymers by a Nanoribbon Mechanism. Angewandte Chemie International Edition, 44, 7964-7968. https://doi.org/10.1002/anie.200502809
- Klok, H.A. and Lecommandoux, S. (2006) Solid-State Structure, Organizationand Properties of Peptide—Synthetic Hybrid Block Copolymers. Advances in Polymer Science, 202, 75-111. https://doi.org/10.1007/12_083