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2 protocols using toluene

1

Synthesis and Characterization of PEG-Containing Copolymers

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Stannous octoate (Sn(Oct)2; 92.5–100%), anhydrous toluene (99.8%), deuterated chloroform (CDCl3; 99.8% D), deuterium oxide (D2O; 99.9% D), lithium chloride (LiCl; 99%) and ε-caprolactone (ε-CL; 97%) were purchased from Sigma-Aldrich. ε-CL was dried under vacuum (0.1 mbar) for 1 h prior to use. α-Methoxy-ω-hydroxy PEG with Mn of 2 kDa (PEG2) and 5 kDa (PEG5) were purchased from Sigma-Aldrich, and 10 kDa (PEG10) from Creative PEG Works. PEG2 and PEG5 were dried at 120 °C under vacuum (0.1 mbar) for 1 h prior to use. Analytical grade diethyl ether, chloroform, toluene, ethyl acetate, N,N-dimethylformamide (DMF), acetone and hexane were purchased from Chem-Supply. All reagents were used as received unless otherwise stated. For DLS experiments, ultrapure water with a resistivity of > 18.2 MΩ.cm was obtained from a Sartorius Arium® ultrapure water purification system. For Synchrotron SAXS experiments, ultrapure water with a resistivity of 18.2 MΩ∙cm, interfacial tension of 72.4 mN∙m−1 at 22°C, and less than 4 ppb of total organic carbon was obtained from a Milli-Q Advantage A10 water purification system.
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2

Synthesis of RAFT-Mediated Polymer Hydrogels

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Poly (ethylene glycol) methyl ether acrylate (PEO MA, average Mn ≈ 480) was purchased from Sigma-Aldrich and used as received. Styrene (Sty, Aldrich, 99%) was passed through a column of Al2O3 to remove the inhibitor. The RAFT agent, 2-[[(butylsulfanyl)-carbonothioyl]sulfanyl] propanoic acid (PABTC), was synthesized as described in ref. 60 (link). 4,4′-azobis(4-cyanovaleric acid) (V501, >98%, Aldrich) was used as received. Acrylamide (AAM, Sigma-Aldrich, ≥98%), N,N′-methylenebisacrylamide (MBAM, Sigma-Aldrich, ≥99.5%)), methanol (Fluka), basic alumina (Al2O3, Brockman activity I, 60–325 mesh), N,N,N′,N′- tetramethylethylenediamine (TEMED, Sigma-Aldrich, 99%), were all used as received. 3-(trimethoxysilyl)propyl methacrylate (γ -MAPS) was obtained from Sigma (St. Louis, MO, USA). Toluene was obtained from Chem-Supply (Gillman, SA, AUS). Potassium persulfate (KPS, M&B, 98%) was recrystallized from water.
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