Issue 6, 2011

Optimization of N-carboxyanhydride (NCA) polymerization by variation of reaction temperature and pressure

Abstract

Several new methods for the controlled ring-opening polymerization of N-carboxyanhydrides (NCA ROP) have been established in the recent past, all of which based on the normal amine mechanism. In this paper the optimal NAM polymerization conditions were investigated combining the high-vacuum and the low-temperature for the NCAs of γ-benzyl-L-glutamate (BLG), Nε-benzyloxycarbonyl-L-lysine (ZLL), L-alanine (Ala), β-benzyl-L-aspartate (BLA), O-benzyl-L-serine (BLS), and O-benzyl-L-threonine (BLT). The polymerizations were followed by FTIR, size exclusion chromatography (SEC) and MALDI-ToF-MS to provide information of the monomer conversion, polymer molecular weight and chain composition as a function of pressure and temperature. It was found that the studied NCAs could be divided into two groups: in the first group monomers of BLG, ZLL and Ala polymerized considerably faster when a lower pressure of 1 × 10−5 bar was applied. MALDI-ToF-MS analysis confirmed that the formation of side products for these monomers mostly started after full monomer conversion. The second group of monomers, i.e. BLA, BLS and BLT, polymerized considerably slower than the first group and no effect was observed from the lower pressure. On the other hand, the number of side reactions was significant at 20 °C, so that the polymerizations for the latter monomers should preferably be done at 0 °C. By combining both methods, multiblock polypeptides were synthesized including a tetrablock of PBLG-b-PAla-b-PZLL-b-PBLA with a polydispersity of 1.3.

Graphical abstract: Optimization of N-carboxyanhydride (NCA) polymerization by variation of reaction temperature and pressure

Supplementary files

Article information

Article type
Paper
Submitted
17 Feb 2011
Accepted
24 Mar 2011
First published
18 Apr 2011

Polym. Chem., 2011,2, 1322-1330

Optimization of N-carboxyanhydride (NCA) polymerization by variation of reaction temperature and pressure

G. J. M. Habraken, K. H. R. M. Wilsens, C. E. Koning and A. Heise, Polym. Chem., 2011, 2, 1322 DOI: 10.1039/C1PY00079A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements