Supporting Information
Facile synthesis of polymer-peptide conjugates via direct amino acid
coupling chemistry
Arun A. Sohdia, Gwen F. Chimonidesa, Mohammad R. Khaleghia, Claire R. Hurleyb, Dave J. Adamsc and
Paul D. Tophama*
a
Chemical Engineering and Applied Chemistry, Aston University, Aston Triangle, Birmingham, B4 7ET, UK.
Tel: +44 (0)121 204 3413; E-mail: p.d.topham@aston.ac.uk
b
Sheffield Surface Analysis Centre, Kroto Research Institute, The University of Sheffield, Sheffield, S3 7HQ.
c
Department of Chemistry, University of Liverpool, Crown Street, Liverpool, L69 7ZD, UK.
GPC, 1H NMR and FTIR characterisation for all conjugates and their corresponding
precursor molecules is provided herein. mPEO7-F4-OEt characterisation data are provided in
the main manuscript. XPS has also been used (Figure S35) to demonstrate the lack of metal
contaminant in our conjugates, using mPEO7-F4-OEt as an exemplar. Prior to this analysis,
Figure S1 shows the GPC traces of the mPEO-COOH materials and their corresponding
hydroxy-terminated precursors. These traces show that the molar masses of the polymers do
not significantly change following oxidation, which is also observed in the integrals in the 1H
NMR spectra of all of these polymers (data not shown).
Figure S1. GPC traces of mPEO7-OH, mPEO12-OH, mPEO17-OH, mPEO7-COOH,
mPEO12-COOH and mPEO17-COOH.
1. mPEO7-based conjugates
1.1 mPEO7-F1-OEt
Figure S2. GPC traces of mPEO7-F1-OEt, mPEO7-COOH and NH3+-F1-OEt.Cl-.
Figure S3. 1H NMR spectra for NH3+-F1-OEt.Cl-, mPEO7-OH, mPEO7-COOH and
mPEO7-F1-OEt, from top to bottom, respectively.
Figure S4. FTIR spectra for mPEO7-OH, mPEO7-COOH, NH3+-F1-OEt.Cl- and
mPEO7-F1-OEt.
1.2 mPEO7-F2-OEt
Figure S5. GPC traces of mPEO7-F2-OEt, mPEO7-COOH and NH3+-F2-OEt.TFA.
Figure S6. 1H NMR spectra for NH3+-F2-OEt.TFA, mPEO7-OH, mPEO7-COOH and
mPEO7-F2-OEt, from top to bottom, respectively.
Figure S7. FTIR Spectra for mPEO7-OH, mPEO7-COOH, NH3+-F2-OEt.TFA and
mPEO7-F2-OEt.
1.3 mPEO7-F3-OEt
Figure S8. GPC traces of mPEO7-F3-OEt, mPEO7-COOH and NH3+-F3-OEt.TFA.
Figure S9. 1H NMR spectra for NH3+-F3-OEt.TFA, mPEO7-OH, mPEO7-COOH and
mPEO7-F3-OEt, from top to bottom, respectively.
Figure S10. FTIR spectra for mPEO7-OH, mPEO7-COOH, NH3+-F3-OEt.TFA and
mPEO7-F3-OEt.
1.4 mPEO7-F4-OEt
Characterisation data for mPEO7-F4-OEt are provided in the main manuscript.
2. mPEO12-based conjugates
2.1 mPEO12-F1-OEt
Figure S11. GPC traces of mPEO12-F1-OEt, mPEO12-COOH and NH3+-F1-OEt.Cl-.
Figure S12. 1H NMR Spectra for NH3+-F1-OEt.Cl-, mPEO12-OH, mPEO12-COOH and
mPEO12-F1-OEt, from top to bottom, respectively.
Figure S13. FTIR Spectra for mPEO12-OH, mPEO12-COOH, NH3+-F1-OEt.Cl- and
mPEO12-F1-OEt.
2.2 mPEO12-F2-OEt
Figure S14. GPC traces of mPEO12-F2-OEt, mPEO12-COOH and NH3+-F2-OEt.TFA.
Figure S15. 1H NMR Spectra for NH3+-F2-OEt.TFA, mPEO12-OH, mPEO12-COOH and
mPEO12-F2-OEt, from top to bottom, respectively.
Figure S16. FTIR Spectra for mPEO12-OH, mPEO12-COOH, NH3+-F2-OEt.TFA and
mPEO12-F2-OEt.
2.3 mPEO12-F3-OEt
Figure S17. GPC traces of mPEO12-F3-OEt, mPEO12-COOH and NH3+-F3-OEt.TFA.
Figure S18. 1H NMR Spectra for NH3+-F3-OEt.TFA, mPEO12-OH, mPEO12-COOH and
mPEO12-F3-OEt, from top to bottom, respectively.
Figure S19. FTIR Spectra for mPEO12-OH, mPEO12-COOH, NH3+-F3-OEt.TFA and
mPEO12-F3-OEt.
2.4 mPEO12-F4-OEt
Figure S20. GPC traces of mPEO12-F4-OEt, mPEO12-COOH and NH3+-F4-OEt.TFA.
Figure S21. 1H NMR Spectra for NH3+-F4-OEt.TFA, mPEO12-OH, mPEO12-COOH and
mPEO12-F4-OEt, from top to bottom, respectively.
Figure S22. FTIR Spectra for mPEO12-OH, mPEO12-COOH, NH3+-F4-OEt.TFA and
mPEO12-F4-OEt.
3. mPEO17-based conjugates
3.1 mPEO17-F1-OEt
Figure S23. GPC traces of mPEO17-F1-OEt, mPEO17-COOH and NH3+-F1-OEt.Cl-.
Figure S24. 1H NMR Spectra for NH3+-F1-OEt.Cl-, mPEO17-OH, mPEO17-COOH and
mPEO17-F1-OEt, from top to bottom, respectively.
Figure S25. FTIR Spectra for mPEO17-OH, mPEO17-COOH, NH3+-F1-OEt.Cl- and
mPEO17-F1-OEt.
3.2 mPEO17-F2-OEt
Figure S26. GPC traces of mPEO17-F2-OEt, mPEO17-COOH and NH3+-F2-OEt.TFA.
Figure S27. 1H NMR Spectra for NH3+-F2-OEt.TFA, mPEO17-OH, mPEO17-COOH and
mPEO17-F2-OEt, from top to bottom, respectively.
Figure S28. FTIR Spectra for mPEO17-OH, mPEO17-COOH, NH3+-F2-OEt.TFA and
mPEO17-F2-OEt.
3.3 mPEO17-F3-OEt
Figure S29. GPC traces of mPEO17-F3-OEt, mPEO17-COOH and NH3+-F3-OEt.TFA.
Figure S30. 1H NMR Spectra for NH3+-F3-OEt.TFA, mPEO17-OH, mPEO17-COOH and
mPEO17-F3-OEt, from top to bottom, respectively.
Figure S31. FTIR Spectra for mPEO17-OH, mPEO17-COOH, NH3+-F3-OEt.TFA and
mPEO17-F3-OEt.
3.4 mPEO17-F4-OEt
Figure S32. GPC traces of mPEO17-F4-OEt, mPEO17-COOH and NH3+-F4-OEt.TFA.
Figure S33. 1H NMR Spectra for NH3+-F4-OEt.TFA, mPEO17-OH, mPEO17-COOH and
mPEO17-F4-OEt, from top to bottom, respectively.
Figure S34. FTIR Spectra for mPEO17-OH, mPEO17-COOH, NH3+-F4-OEt.TFA and
mPEO17-F4-OEt.
A typical XPS survey spectrum of mPEO7-F4-OEt is shown in Figure S35. The survey
spectrum shows the elemental composition of the surface excluding hydrogen and
demonstrates the absence of metal contaminant in the final conjugates. Various samples were
taken from the same product, revealing near-identical spectra. The lack of chromium in our
samples is proven by the absence of the peak at the binding energies indicated by the black
lines in the spectrum.
wide/8
x 10
3
Cr L MM
Cr 2s
80
FWH M
3.197
3.481
2.638
3.229
2.617
A rea
76.06
126.87
15.20
2.81
3.62
A t%
17.63
74.11
5.29
0.48
2.49
C 1s
P os .
532.00
285.00
400.00
688.00
102.00
Cr 3s
Cr 3d5/2
Cr 3p1/2
Cr 3p3/2
Cr 3p Cr 3d3/2
Cr 3d
O 1s
70
N ame
O 1s
C 1s
N 1s
F 1s
Si 2p
Cr 2p1/2
Cr 2p3/2
Cr 2p
60
CPS
50
40
F 1s
N 1s
30
20
Si 2p
10
0
1200
900
600
Bindi ng E nergy (eV)
300
0
Figure S35. XPS Survey Spectrum of mPEO7-F4-OEt, where the black lines have been
included to indicate the positions of the chromium peaks.