Supporting Information
RAFT made methacrylate copolymers for reversible
pH-responsive nanoparticles
Turgay Yildirim,a,b Alexandra C. Rinkenauer,a,b Christine Weber,a,b Anja Traeger,a,b Stephanie
Schubert,b,c Ulrich S. Schubert*,a,b
a
Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University
Jena, Humboldtstr. 10, 07743 Jena, Germany
b
Jena Center for Soft Matter (JCSM), Friedrich Schiller University Jena, Philosophenweg 7,
07743 Jena, Germany
c
Institute of Pharmacy, Department of Pharmaceutical Technology, Friedrich Schiller University
Jena, Otto-Schott-Str. 41, 07745 Jena, Germany
S1
Figure SI-1 Overlay of the SEC traces (CHCl3) from kinetic studies of the RAFT copolymerization of MMA with
10% comonomer: DMAEMA (P1), tBAEMA (P3) and AEMA·HCI (P5). [M]/[CPADB]/[AIBN] = 100/1/0.25; [M]0
= 2 mol L-1. Polymerization conditions for (P1 and P3): Solvent ethanol, T = 70 °C. Polymerization conditions for
P5: Solvent methanol under reflux.
Figure SI-2 Kinetic studies of the RAFT copolymerization of MMA with 20 mol% comonomer DMAEMA (P2),
tBAEMA (P4) and AEMA·HCI (P6). [M]/[CPADB]/[AIBN] = 100/1/0.25; [M] 0 = 2 mol L-1. Polymerization
conditions for (P2 and P4): Solvent ethanol, T = 70 °C. Polymerization conditions for P6: Solvent methanol under
reflux. (A) Semilogarithmic kinetic plots. (B) Mn and Mw/Mn evolution with total monomer conversion. (C) SEC
overlay traces (CHCl3).
S2
Figure SI-3 Normalized SEC traces (DMAc, RI detection) of the isolated copolymers of P1-P6.
Figure SI-4 Normalized SEC traces (CHCl3, RI detection) of the isolated copolymers P5 and P7.
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Figure SI-5 Normalized SEC traces (DMAc, RI detection) of isolated copolymers P5 and P7.
Figure SI-6 Normalized SEC traces (CHCl3, RI detection) of isolated copolymers P6 and P8.
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Figure SI-7 Normalized SEC traces (DMAc, RI detection) of isolated copolymers P6 and P8.
Figure SI-8 1H NMR spectrum (300 MHz, CDCl3) of P1.
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Figure SI-9 1H NMR spectrum (300 MHz, CDCl3) of P2.
Figure SI-10 1H NMR spectrum (300 MHz, CDCl3) of P3.
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Figure SI-11 1H NMR spectrum (300 MHz, CDCl3) of P4.
Figure SI-12 1H NMR spectrum (300 MHz, CDCl3) of P5.
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Figure SI-13 1H NMR spectrum (300 MHz, MeOD) of P6.
Figure SI-14 1H NMR spectrum (300 MHz, CDCl3) of P7.
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Figure SI-15 1H NMR spectrum (300 MHz, CDCl3) of P8.
Figure SI-16 SEM images of nanoparticles that were prepared from P2, P4 and P8 (1 mg mL-1) by dropping
acetone-polymer solution to water (AW) or dropping water to acetone-polymer solution (WA).
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Figure SI-17 SEM images of nanoparticles that were prepared from P1 and P2 (10 mg mL-1) by dropping acetonepolymer solution to water (AW) or dropping water to acetone-polymer solution (WA).
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Figure SI-18 SEM images of nanoparticles that were prepared from P7 and P8 (10 mg mL-1) by dropping acetonepolymer solution to water (AW) or dropping water to acetone-polymer solution (WA).
Figure SI-19 (A) Z-Average diameter (represented up to 1000 nm) and PDI values of Eudragit E100 nanoparticles
as a function of the pH value. (B) Zeta potential of the Eudragit E100 nanoparticles as a function of the pH value.
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Figure SI-20 Fluorescence emission spectra of pyrene (6 × 10 -5 mol L-1) with P8 nanoparticles (0.15 mg mL-1) at
various pH values. Pyrene in pure water was used as control.
Table SI-1 C, H, N, S and Cl contents (mass % in dry sample) in the copolymers of P5, P6, P7 and P8 that were
determined by elemental analysis.
Polymer
P5
P7
P6
P8
C
56.30
58.31
52.97
55.80
H
7.86
8.00
7.85
7.75
N
1.73
1.73
2.95
3.02
S
0.81
0.85
0.94
0.89
Cl
3.03
1.01
4.92
0.92
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