2 isocyanatoethyl methacrylate

The different types of chemicals and modifiers used in this study are as follows: maleic anhydride (MAH, 95%, Sigma-Aldrich, St. Louis, MO, USA) and 2-Isocyanatoethyl methacrylate (IEM, 98%, Sigma-Aldrich, St. Louis, MO, USA) are used as functional groups; ceric ammonium nitrate (CAN, Sigma-Aldrich, St. Louis, MO, USA); dicumyl peroxide (DCP, 98%, Fisher, Portsmouth, NH, USA) is used as an initiator, acetone (99%, Sigma-Aldrich, St. Louis, MO, USA) is used as a solvent. All the chemicals were used as received without any modification, and all the functionalisation experiments were performed in a heterogenous mixture (polymer and/or filler and solvent) in a round bottom flask with a magnetic stirrer equipped with a condenser.

Chemical
and physical characterizations were performed using Shimadzu TGA-50,
Shimadzu DTA-50, Shimadzu DSC-60, Park Systems XE-100E AFM, LEO-EVO
40× SEM, Bruker NMR 300 MHz Ultrashield, Ascend 600 ULW, and
PerkinElmer UATR Two FTIR devices. All spectrophotometric analyses
were carried out with a Shimadzu UV-1601 UV–visible spectrophotometer
and BioTek Eon Elisa microplate reader. The adhesion results were
obtained with an MTS E42 test analyzer. L-929 cell morphologies were
determined by a JuliFL cell analyzer and an Olympus CKX41 inverted/fluorescence
microscope. Histological analysis was carried out with Leica DFC-280
microscope and Leica Q Win Image Analyze System (Leica Micros Imaging
Solutions Ltd., Cambridge, UK).
Polyethylene glycol 200 (PEG200),
polyethylene glycol 400 (PEG400), and polyethylene glycol 600 (PEG600)
were purchased from Merck. 4,4′-Methylenebis cyclohexyl diisocyanate,
β-cyclodextrin, silk sericin (10–40 kDa), toluene-4-sulfonyl
isocyanate, tetrabutylammonium hydroxide, MTT (thiazolyl blue tetrazolium
bromide), Dulbecco’s modified Eagle’s medium (DMEM),
gentamicin sulfate, and 2-isocyanatoethyl methacrylate were purchased
from Sigma-Aldrich. DMSO, acetonitrile, methanol, ethanol, and other
solvents were obtained from Merck. Irgacure-2959 was purchased from
TCI (Tokyo Chemical Industry). All chemicals were used without further
purification.

N,N-Dimethylformamide (DMF; Sigma-Aldrich, ≥99.9%) was dried over molecular sieves. α,α′-Azoisobutyronitrile (AIBN; Ventron) was re-crystallised from methanol. Monomethacryloxypropyl terminated polydimethylsiloxane (PDMSMA MCR-M07; Gelest, 703.3 g mol⁻¹ as determined by ¹H NMR), 2-isocyanatoethyl methacrylate (Sigma-Aldrich, 98%), 2-amino-4-hydroxy-6-methylpyrimidine (Sigma-Aldrich, 98%), iron (ii, iii) oxide powder (Fe₃O₄; Sigma-Aldrich, size < 5 μm, 95%), tetrahydrofuran (THF; Sigma-Aldrich, 99.9%), methanol (Sigma-Aldrich, 99.9%), dimethyl sulfoxide (DMSO; SAFC, ≥99%), 1,4-dioxane (Sigma-Aldrich, 99.8%), and THF-d₈ (Sigma-Aldrich, 99.8 atom% D) were used as received. 6-Methyl-2-ureido-4[1H]-pyrimidone-bearing methacrylate (UPyMA) was synthesised as reported in the literature.^{15 (link)}

Poly(ethylene glycol) methyl ether methacrylate (OEGMA, M_n ≈ 475 g/mol, 98%), 2-Cyano-2-propyl 4-cyanobenzodithioate (CPCBD, 98%), 2,2′-azobis (2-methylpropionitrile) (AIBN, 98%), 6-Methylisocytosine (MIC, 98%) and 2-Isocyanatoethyl methacrylate (98%) were purchased from Sigma-Aldrich. OEGMA was purified by passing through basic alumina. SWNTs with carboxyl functionalization (1–2 nm outside diameter, 3 wt% COOH groups) was purchased from SkySpring Nanomaterials.

Bisphenol A glycidyl dimethacrylate (BisGMA), 2 hydroxyethyl methacrylate (HEMA), Camphoroquinone (CQ), Ethyl-4(dimethylamino) benzoate (EDMAB), and Diphenyliodonium hexafluorophosphate (DPIHP), 2-isocyanatoethyl methacrylate, and 2-butanone were procured from Sigma Aldrich, Inc. St. Louis, MO, US. Sodium hydroxide (NaOH) and methacryloxypropyl (trimethoxy) silane were procured from Fischer Scientific and Gelest Inc., Waltham, MA, USA, respectively.