Modulating Antimicrobial Activity and Mammalian Cell Biocompatibility ...
Supporting Information
Modulating Antimicrobial Activity and Mammalian Cell Biocompatibility
with
Glucosamine-functionalized
Star
Polymers Edgar H. H. Wong,*†a,b Mya Mya Khin,a,b Vikashini Ravikumar,c Zhangyong Si,a,b Scott A. Ricec,d and Mary B. Chan-Park*a,b a
School of Chemical and Biomedical Engineering, Nanyang Technological University,
Singapore 637459. b
Centre for Antimicrobial Bioengineering, Nanyang Technological University, Singapore
637459. c
The Singapore Centre for Environmental Life Sciences Engineering, Nanyang Technological
University, Singapore 637551. d
School of Biological Sciences, Nanyang Technological University, Singapore 637551.
† Present address: Centre for Advanced Macromolecular Design and Australian Centre for Nanomedicine, School of Chemical Engineering, The University of New South Wales, Sydney, NSW 2052, Australia. Author correspondence: [email protected]; [email protected]
1. Supplementary Results
Figure S1. 13C NMR spectra of acrylate-functionalized D-glucosamine peracetate monomer.
Figure S2. 1H NMR spectra of glucosamine-based linear homopolymer prepared via RAFTbased photopolymerization.
Figure S3. 1H NMR spectra of L-pGSA macroinitiator prepared via iterative RAFT-based photopolymerization.
Figure S4. GPC DRI chromatograms of polyglucosamine-based macroinitiator and its precursor.
Figure S5. 1H NMR spectra of RAFT-functionalized poly(Z-L-lysine) prepared via tandem NCA-ROP and CuAAC.
Figure S6. 1H NMR spectra of L-pLYS macroinitiator that contains the peptide and poly(HEAm) spacer blocks.
Figure S7. GPC DRI chromatograms of poly(Z-L-lysine) macroinitiator and its precursors.
Figure S8. 1H NMR spectra of star polymers S-pLYS and S-LYS.
Figure S9. 1H NMR spectra of star polymers S-pGSA 25 and S-GSA 25.
Figure S10. 1H NMR spectra of star polymers S-pGSA 50 and S-GSA 50.
Figure S11. 1H NMR spectra of star polymers S-pGSA 65 and S-GSA 65.
Figure S12. 1H NMR spectra of star polymers S-pGSA 100 and S-GSA 100.
Figure S13. (a) GPC DRI chromatogram of PZLL-based star polymer S-pLYS. (b) DLS normalized volume distribution of S-LYS star after deprotection. Noteworthy, the broad peak at larger diameter is due to the star-star coupled product.
Table S1. Physical characterization of the macroinitiator precursors and star polymer. Entry
a
Mna (g mol-1)
Ɖa
% conv.b
Narmc
dH
ζ
(nm)
(mV)
PZLL-yne
3800
1.5
–
–
–
–
PZLL-RAFT
4100
1.6
–
–
–
–
L-pLYS
13800
1.6
–
–
–
–
PGSA
7700
1.2
–
–
–
–
L-pGSA
15200
1.4
–
–
–
–
S-LYS
239000
3.5
60
18
24.0
44.4
Determined based on the protected forms via a GPC-DMF system using narrow
polystyrene standards as the reference. The Mn (and hence Narm) values are relative to a polystyrene calibration and are estimates of the actual molecular weights. bRefers to the conversion of macroinitiator to high star. cEstimated based on literature protocol.
Figure S14. Comparison of the 1H NMR spectra between L-pLYS and L-LYS following the removal of carboxybenzyl protecting groups.
Figure S15. Comparison of the 1H NMR spectra between L-pGSA and L-GSA following the removal of acetyl protecting groups.
Figure S16. Percentage of living AoSMC after 24 h incubation with different polymer samples and at sample concentrations of 100 and 500 μg mL-1. The control sample is the physical blend of L-LYS and L-GSA at 75:25 molar ratio, which mimics the chemical composition of the glycosylated miktoarm star polymer S-GSA 25. The control sample has less than half the number of living SMC cells compared S-GSA 25 even though both samples are almost identical in chemical composition, thus demonstrating the advantage of the miktoarm star architecture in providing mammalian cell biocompatibility.
Figure S17. Self-constructed photoreactor made from blue LED lights wound around the inside of a plastic beaker that was employed in all RAFT-based photopolymerization reactions described in this study.
Figure S18. DLS autocorrelation function plots for the distributions shown in Figure 3b.
Modulating Antimicrobial Activity and Mammalian Cell Biocompatibility
with
Glucosamine-functionalized
Star
Polymers Edgar H. H. Wong,*†a,b Mya Mya Khin,a,b Vikashini Ravikumar,c Zhangyong Si,a,b Scott A. Ricec,d and Mary B. Chan-Park*a,b a
School of Chemical and Biomedical Engineering, Nanyang Technological University,
Singapore 637459. b
Centre for Antimicrobial Bioengineering, Nanyang Technological University, Singapore
637459. c
The Singapore Centre for Environmental Life Sciences Engineering, Nanyang Technological
University, Singapore 637551. d
School of Biological Sciences, Nanyang Technological University, Singapore 637551.
† Present address: Centre for Advanced Macromolecular Design and Australian Centre for Nanomedicine, School of Chemical Engineering, The University of New South Wales, Sydney, NSW 2052, Australia. Author correspondence: [email protected]; [email protected]
1. Supplementary Results
Figure S1. 13C NMR spectra of acrylate-functionalized D-glucosamine peracetate monomer.
Figure S2. 1H NMR spectra of glucosamine-based linear homopolymer prepared via RAFTbased photopolymerization.
Figure S3. 1H NMR spectra of L-pGSA macroinitiator prepared via iterative RAFT-based photopolymerization.
Figure S4. GPC DRI chromatograms of polyglucosamine-based macroinitiator and its precursor.
Figure S5. 1H NMR spectra of RAFT-functionalized poly(Z-L-lysine) prepared via tandem NCA-ROP and CuAAC.
Figure S6. 1H NMR spectra of L-pLYS macroinitiator that contains the peptide and poly(HEAm) spacer blocks.
Figure S7. GPC DRI chromatograms of poly(Z-L-lysine) macroinitiator and its precursors.
Figure S8. 1H NMR spectra of star polymers S-pLYS and S-LYS.
Figure S9. 1H NMR spectra of star polymers S-pGSA 25 and S-GSA 25.
Figure S10. 1H NMR spectra of star polymers S-pGSA 50 and S-GSA 50.
Figure S11. 1H NMR spectra of star polymers S-pGSA 65 and S-GSA 65.
Figure S12. 1H NMR spectra of star polymers S-pGSA 100 and S-GSA 100.
Figure S13. (a) GPC DRI chromatogram of PZLL-based star polymer S-pLYS. (b) DLS normalized volume distribution of S-LYS star after deprotection. Noteworthy, the broad peak at larger diameter is due to the star-star coupled product.
Table S1. Physical characterization of the macroinitiator precursors and star polymer. Entry
a
Mna (g mol-1)
Ɖa
% conv.b
Narmc
dH
ζ
(nm)
(mV)
PZLL-yne
3800
1.5
–
–
–
–
PZLL-RAFT
4100
1.6
–
–
–
–
L-pLYS
13800
1.6
–
–
–
–
PGSA
7700
1.2
–
–
–
–
L-pGSA
15200
1.4
–
–
–
–
S-LYS
239000
3.5
60
18
24.0
44.4
Determined based on the protected forms via a GPC-DMF system using narrow
polystyrene standards as the reference. The Mn (and hence Narm) values are relative to a polystyrene calibration and are estimates of the actual molecular weights. bRefers to the conversion of macroinitiator to high star. cEstimated based on literature protocol.
Figure S14. Comparison of the 1H NMR spectra between L-pLYS and L-LYS following the removal of carboxybenzyl protecting groups.
Figure S15. Comparison of the 1H NMR spectra between L-pGSA and L-GSA following the removal of acetyl protecting groups.
Figure S16. Percentage of living AoSMC after 24 h incubation with different polymer samples and at sample concentrations of 100 and 500 μg mL-1. The control sample is the physical blend of L-LYS and L-GSA at 75:25 molar ratio, which mimics the chemical composition of the glycosylated miktoarm star polymer S-GSA 25. The control sample has less than half the number of living SMC cells compared S-GSA 25 even though both samples are almost identical in chemical composition, thus demonstrating the advantage of the miktoarm star architecture in providing mammalian cell biocompatibility.
Figure S17. Self-constructed photoreactor made from blue LED lights wound around the inside of a plastic beaker that was employed in all RAFT-based photopolymerization reactions described in this study.
Figure S18. DLS autocorrelation function plots for the distributions shown in Figure 3b.
