Acryloyl chloride

The l-Alaninamide hydrochloride was purchased from Ark Pharm (Libertyville, IL, USA). Acryloyl chloride, potassium carbonate, 2-propanol, acetone, methanol, diethyl ether, and dichloromethane were supplied by Aldrich (Saint-Quentin, Fallavier, France). Glycinamide hydrochloride was obtained from Acros Organics Fisher Scientific (Illkirch, France). Di-potassium peroxodisulfate was used as received from VWR (Fontenay-sous-Bois, France). The isoosmolar pH = 7.4/320 mOsm phosphate buffer was made by mixing 3.31 g of NaH₂PO₄·H₂O and 33.77 g of Na₂HPO₄·7H₂O in 1 dm³ of water. Spectra/Por® membranes were supplied by Roth Sochiel (Lauterbourg, France). The N-acryloyl glycinamide was synthesized as reported in our previous study [21 (link)].

Acetone and ethanol were purchased from Carl Roth. Acetonitrile, 2,2-dimethoxypropane, p-toluenesulfonic acid, tetrahydrofuran and sodium chloride (98%) were purchased from Sigma Aldrich (Taufkirchen, Germany). Acryloyl chloride (96%) was purchased from Merck (Darmstadt, Germany). Azobis(isobutyronitril) (98%), triethylamine and trifluoroacetic acid were purchased from Acros Organics (Geel, Belgium). Dichlormethane, diethylether, ethyl acetate, methanol, hexane and dimethylformamide were purchased from VWR Prolabo (Darmstadt, Germany). Dopamine hydrochloride (99.96%) and glycinamide hydrochloride were purchased from BLD Pharmatech (Kaiserslautern, Germany). Hydroquinone was purchased from J.T. Baker (Phillipsburg, NJ, USA). Potassium carbonate, lithium hydroxide and magnesium sulfate were purchased from Fisher Scientific. Methyl trifluoroacetate was purchased from Fluorochem (Hadfield, UK). N-[3-(Dimethylamino)propyl]acrylamide (98%) and N-(2-hydroxyethyl)acrylamide (98%) were purchased from TCI (Tokyo, Japan). Sodium hydrogencarbonate, hydrochloric acid (37%) and toluene were purchased from VWR Chemicals.

Gelatin from porcine skin, poly(ε-caprolactone) (PCL with M̄_n = 80 000 g mol⁻¹), a dialysis bag with a cut-off of 12 kDa, Hoechst dye and 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyl tetrazolium bromide (MTT powder) were purchased from Sigma-Aldrich. Poly(ethylene glycol) (PEG, M̄_n = 1000 g mol⁻¹), acryloyl chloride, methacrylic anhydride, sodium hydroxide, diethyl ether, ethanol, and DMSO were obtained from Merck. Ammonium persulfate (APS), potassium dihydrogen phosphate (KH₂PO₄), and ethylenediaminetetraacetic acid (EDTA) were prepared from Fluka. Toluene and acetone were provided by Dr Mojallali Co. Coconut oil as the internal phase was obtained from the market. Distilled water was freshly used for all the experiments.

Amino acids tyrosine and tryptophan (99% and 97% Acros, Düsseldorf, Germany), (AIBN, 98% Acrōs Germany) 2,2′-azobis(isobutyronitrile) were recrystallized from methanol, and N-isopropylacrylamide (NIPAAm, Düsseldorf) was recrystallized from distilled hexane. Vanillin (99% Düsseldorf, Germany), triethylamine (99% Merck, Darmstadt, Germany), acryloyl chloride (98% Merck, Darmstadt, Germany), formaldehyde (38% Sigma-Aldrich, Darmstadt, Germany), diethyl amine (99% Acros, Düsseldorf, Germany), Dichloromethane, dioxane, tetrahydrofuran (THF), and diethyl ether were distilled over potassium hydroxide. Other chemicals were used as received. For pH 1.68, pH 7 and pH 12.46 buffer solutions were used as purchased from Thermo Fisher (Loughborough, US).

Pluronic F127 (MW = 12,600, 70% PEG, composition confirmed with proton (¹H) nuclear magnetic resonance (NMR) spectroscopy), allyl bromide, sodium hydride, 2,2′-Azobis(2-methylpropionitrile) (AIBN), thioacetic acid (purum, ≥ 95.0% (GC)), Tetronic 701 (MW = 3600, 10% PEG), acryloyl chloride (purity: 97.0%, contains <210 ppm MEHQ as stabilizer), triethylamine (purity ≥ 99.5%), tris(2-carboxyethyl)phosphine hydrochloride (TCEP) (purity 98%), sodium hydroxide (purity ≥ 97%, pellets), hydrochloric acid (37%), potassium phosphate monobasic, sodium phosphate dibasic, toluene, N,N-Dimethylformamide, ammonium persulfate (APS), tetramethylethyldiamine (TEMED), and ibuprofen (purity 98%) were purchased from Merck (Sigma-Aldrich, Milan, IT, USA) and used as received.
All the functionalized polymers obtained were characterized using a 400 MHz Bruker ¹H NMR spectrometer and a Thermo Scientific Nicolet iS50 Fourier-transform infrared (FT-IR) spectrometer in Attenuated total reflection (ATR) mode. Dynamic light scattering (DLS) measurements were carried out with Malvern Zetasizer ZS (Malvern, UK). Size Exclusion Chromatography (SEC) analysis was performed with the Jasco GPC System in tetrahydrofuran (THF) at a flow rate of 1 mL/min at 35 °C, calibrated using polystyrene standards.

3,5-Bis(2-dodecylthiocarbonothioylthio-1-oxopropoxy)benzoic acid (BTCBA, 98%), 2-(Dodecylthiocarbonothioylthio)propionic acid (DTPA, 98%), acryloyl chloride (≥97%), triethylamine (TEA, ≥99%), 2-methyltetrahydrofuran (Me-THF, 99.5%), n-Butyl acrylate (BA, 99%), butyl l-lactate (98%) were all purchased from Merck KGaA (Darmstadt, Germany) and used as received unless otherwise specified. Thus, BA was passed through a short column of basic Al₂O₃ prior to use in order to remove the radical inhibitor and both TEA and Me-THF were distilled prior to use from CaH₂ and sodium/benzophenone, respectively. 2,2′-Azobis(2-methylpropionitrile) [AIBN, ≥98%, Fluka (Buchs, Switzerland)] was recrystallized three times from methanol before further use. Deuterated chloroform (CDCl₃) was purchased from Eurisotop, and ethyl-5-(dimethylamido)-2-methyl-5-oxopentanoate (Rhodiasolv^® PolarClean) was kindly donated by Solvay (Aubervilliers, France). Isosorbide acetate, i.e., isosorbide 2-acrylate-5-acetate and vanillin acrylate monomers were prepared following previously reported synthetic procedures [32 (link),33 (link),34 (link)].