Furfuryl isocyanate

Amorphous propylene oxide trismaleimide (3M, M_eq = 249 g mol⁻¹, f = 2.65) is purchased from Specific Polymers. Glycerol-based polyol Daltolac R630 (M = 267 g mol⁻¹) is supplied by Huntsman. Poly(propylene glycol) methacrylate (PPG375-MA, M = 375 g mol⁻¹, 97%), furfuryl isocyanate (M = 123 g mol⁻¹), dibutyl tin dilaurate (DBTDL, catalyst) and phenylbis(2,4,6-trimethylbenzoyl) phosphine oxide or bisacyl phosphine oxide (BAPO, 97%, powder, photoinitiator) are purchased from Sigma Aldrich. Daltolac R630 is dried over molecular sieves (4 Å), all other materials are used as received. 3M is stored at 4 °C under inert gas atmosphere. furfuryl isocyanate is stored at 4 °C. Chemical structures of all products are shown in Figure 2.

Furfuryl isocyanate (Sigma-Aldrich (Saint Louis, MO, USA), 97%), 6-maleimidohexanoic acid (Sigma-Aldrich, 98%), Benzocaine (Sigma-Aldrich, Pharmaceutical Secondary Standard), sodium periodate (NaIO₄, Sigma-Aldrich, 99%), N-(3-dimethylaminopropyl)-N-ethylcarbodiimide hydrochloride (EDC, Sigma-Aldrich, 99%), 4-(dimethylamino)pyridine (DMAP, Sigma-Aldrich, 99%), ethanol (Sigma-Aldrich, anhydrous), N,N-dimethylformamide (Sigma-Aldrich), hydroxylamine hydrochloride (NH₂OH·HCl, Sigma-Aldrich, 99%), hydrochloric acid (HCl, Sigma-Aldrich, 37% aqueous solution), aqueous suspension of cellulose nanocrystals with concentration 10 wt% obtained by sulfuric acid hydrolysis (CNC, University of Maine Process Development) and Hank’s Balanced Salt Solution (HBSS, 1×, without calcium and magnesium ions, Life Technologies, Thermo Fisher Scientific, Carlsbad, CA, USA) were used as received without purification. For dialysis, cellulose-based dialysis bags with a 12 kDa molecular weight cutoff were used.

Monomethacryloxypropyl-terminated polydimethylsiloxane macromonomers (MCR-M11: M_n ~ 1000 g/mol, $n_{sc}$ 14, and MCR-M17: M_n ~ 5000 g/mol, $n_{sc}$ 70) were obtained from Gelest and purified using basic alumina columns to remove inhibitor. Aminopropyl terminated polydimethylsiloxane (DMS-A15, M_n~3,000 g/mol), trimethylsiloxy terminated polydimethylsiloxane (DMS-T72, M_n ~ 500,000 g/mol), and chlorine terminated polydimethylsiloxane (DMS-K05, M_n ~ 425–650 g/mol) were purchased from Gelest and used as received. PEGMA macromonomer (M_n ~ 500 g/mol) was obtained from Sigma-Aldrich and purified using basic alumina columns to remove inhibitor. Ethylene bis(2-bromoisobutyrate) (2f-BiB), tris[2-(dimethylamino)ethyl]amine (Me6TREN), Copper(I) chloride (CuCl), Copper(I) bromide (CuBr), triethylamine (TEA), methanesulfonyl chloride, tris(hydroxypropyl)phosphine (THPP), Sodium azide, isophorone diisocyanate (IPDI), and Tin(II) 2-ethylhexanoate, furfuryl isocyanate, maleic anhydride, furan, ethanolamine, isocyanatoethyl methacrylate were purchased from Sigma-Aldrich and used as received. Toluene, anisole, isopropanol, dichloromethane (DCM), N,N-dimethylformamide (DMF), and tetrahydrofuran (THF) were purchased from VWR Chemicals and used as received.