Toluene

Cadmium oxide powder (CdO, 99.5%), selenium powder (Se, ≥ 99.5%), trioctylphosphine (TOP, tech. grade, 90%), and 1-octadecence (ODE, tech. grade, 90%) were purchased from Sigma–Aldrich (St. Louis, MO, USA). Oleic acid (OA), methanol, acetone, toluene, and chloroform were purchased from Daejung. All chemicals were used as received.

C1Q_SBA, C8Q_SBA, and C18Q_SBA were prepared using a previously reported method^{35 (link)}. Briefly, C1Q_SBA was prepared according to the following procedure: 0.1 mol of trimethyl[3-(trimethoxysilyl)propyl]ammonium chloride (50% in methanol, Tokyo Chemical Industry, Tokyo, Japan) and 6 g of SBA (Sigma Aldrich, MO, USA) were stirred for 1 h in 100 mL of toluene (99.5%, Daejung, Siheung, Republic of Korea). The mixture was then refluxed with 1 mL of deionized (DI) water at 100 °C for 48 h. Next, the slurry was treated with 0.1 M NaCl, separated using a 0.45-μm polyvinylidene fluoride (PVDF) filter, and dried at 65 °C in a drying oven until use. C8Q_SBA and C18Q_SBA were also prepared using the same processes as that employed for C1Q_SBA; the difference was that dimethyloctyl[3-(trimethoxysilyl)propyl]ammonium chloride and dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (42% in methanol, Sigma Aldrich, MO, USA), respectively, were used instead of trimethyl[3-(trimethoxysilyl)propyl]ammonium chloride. Dimethyloctyl [3-(trimethoxysilyl)propyl]ammonium chloride was synthesized by reacting 0.1 mol of (3-chloropropyl)trimethoxysilane (≥ 97%, Sigma Aldrich, MO, USA) and 0.1 mol of N,N-dimethyloctylamine (95%, Sigma Aldrich, MO, USA) at 85 °C for 48 h.

Potassium hexacyanocobaltate(III) (K₃[Co(CN)₆]; ≥97%), anhydrous TBA (≥99.5%), poly(ethylene glycol)-b-poly(propylene glycol)-b-poly(ethylene glycol) (Pluronic^® P-123; molecular weight (MW) ≈ 5800), ethylene glycol (EG; ≥99%), and glycerol (GL; ≥99%) were purchased from Merck Korea (Seoul, Korea) and used without further purification. Anhydrous zinc chloride (ZnCl₂; >98%), CL (99%), and VL (99%) were obtained from Fisher Scientific Korea Ltd. (Incheon, Korea). Polypropylene glycol (PPG; MW = 400 with functionality (F) = 2) obtained from Kumho Petrochemical Co. (Ulsan, Korea) were used as received. Reagent grades of Ac, DMAc, DMF, DMSO, NMe, NMP, toluene, chloroform, and diethyl ether were purchased from Dae Jung Chemical Co. (Gyeonggi-do, Korea) and were distilled prior to use. Polymerization grade PO, obtained from Mitsui Chemicals and SKC Polyurethanes Inc. (Ulsan, Korea), was dried over calcium hydride.

Ammonium metatungstate hydrate (AMT), oleylamine, and 3-(trimethoxysilyl)propyl methacrylate(TMSPMA) were purchased from Sigma–Aldrich. Sodium hydroxide (NaOH) was purchased from Samchun Chemical. Toluene and acetone were purchased from DaeJung chemicals. White 100% polyester fabric (microfiber) was purchased from Dou fabric.

Anhydrous N,N-dimethylformaide (Sigma-Aldrich, St. Louis, MO, USA), N-carboxy anhydrides of l-alanine (Onsolution, Seoul, Korea), α-amino-ω-methoxy-poly(ethylene glycol)s (PEG) (Mn = 2000 Da) (Pharmicell, Seoul, Korea), Diethyl ether (Daejung, Siheung, Korea), and Deuterium oxide (D₂O), Trifluoroacetic acid-d (CF₃COOD) (Sigma-Aldrich, USA) were purchased and used as received. Toluene (Daejung, Korea) was dehydrated by sodium. Chloroform (Daejung, Korea) was dried over magnesium sulfate. Sodium Hyaluronate (HA) (Mn = 14,800 Da) was purchased from Lifecore biomedical (Chaska, MN, USA). Human adipose-derived mesenchymal stem cells (hADSCs) and breast cancer cells (MDA-MB-231) were received from Cefobio (Seoul, Korea) and Korean Cell Line Bank (Seoul, Korea), respectively. RPMI-1640, fetal bovine serum (FBS) and penicillin/streptomycin (PS) were purchased from Hyclone (South Logan, UT, USA). 0.25% trypsin, 2.21mM EDTA, 1X sodium was purchased from Corning (Corning, NY, USA). 3-(4,5-Dimethylthiazol-2-yl)-2,5-Diphenyltetrazolium Bromide (MTT) and live/dead viability cytotoxicity kit were purchased from Invitrogen (Carlsbad, CA, USA).

The ESBR and RAFT ESBR were used after coagulating latex with NaCl and H₂SO₄. Carbon black N330 (OCI, Korea) was used as a filler when manufacturing the carbon black-filled compound. Zinc oxide (ZnO) and stearic acid (CH₃(CH₂)₁₆COOH) as additives, N-(1,3-dimethybutyl)-N’-phenyl-phenylenediamine (6PPD) as an antioxidant, sulfur, N-cyclohexyl benzothiazyl sulfenamide (CBS), and diphenyl guanidine (DPG) as vulcanization agents, were purchased from Merck, Kenilworth, NJ, USA.
Tetrahydrofuran (THF, Daejung, Korea) and n-hexane (Daejung, Busan, Korea) were used in order to remove organics from the vulcanizates prior to the swelling experiments. Toluene (Daejung, Korea) was used to confirm the crosslink density. Piperidine (Daejung, Korea), propane-2-thiol (Acros Organics, Waltham, MA, USA), and n-heptane (Samchun, Seoul, Korea) were used to destroy the vulcanizates structure.