4 methoxyphenol

Terephthalic acid (purity ≥99%) was purchased from Acros Organics and butyltin hydroxide oxide hydrate (97%) from Sigma-Aldrich. 1,4-Cyclohexanedimethanol (>99%) with 70% of the trans isomer, dimethyl terephthalate (DMT, >99%) were purchased from TCI. Isosorbide was acquired from Roquette Frères (≥99.9%). 2,5-Furandicarboxylic acid (FDCA, >99.5%) was provided by Avantium.
p-Cresol (4-methyl phenol, >99%), guaiacol (2-methoxy phenol, >99%) and 4-chlorophenol (>99%) were purchased from ACROS Organics, 4-ethyl phenol (98%), 4-methoxyphenol (99%) and dimethoxybenzene (99%) from Sigma Aldrich and 4-ethyl guaiacol (4-ethyl-2-methoxyphenol, 97%) from ABCR.

The methacrylate conjugation to gelatin was accomplished following a previously published method [22 (link),23 (link),34 (link)]. In a typical experimental set-up, gelatin (10 g, Sigma Aldrich, St. Louis, MO, USA), 4-dimethylaminopyridine (1 g, Sigma Alrdich), and 4-methoxyphenol (0.1g, Sigma Aldrich), were dissolved in 100 mL dimethylsulfoxide at 50 °C. Then, glycidyl methacrylate (4 mL, Sigma Aldrich) was slowly added and reacted for 2 days at 50 °C under dry N₂. The product was purified by dialysis against deionized water for 2 days, changing the water three times a day, and dried by lyophilization. The chemical structure of the product was analyzed using ¹H-NMR spectroscopy (Figure S1, Supplementary Materials).

Tetraethylorthosilicate (TEOS) 99%, (3-glycidoxypropyl)trimethoxysilane (Gly) 98%, divinylbenzene (DVB) technical grade 80%, containing monomethyl ether hydroquinone as inhibitor, 4-vinylpiridine (4-VP) 95%, containing 100 ppm hydroquinone as inhibitor, methacrylic acid, (MA) 99% stabilized with 250 ppm 4-methoxyphenol, aluminium oxide (Al₂O₃), and 2,2′-Azobis(2-methylpropionitrile) (AIBN) 98% were purchased from Sigma-Aldrich (Merck, KGaA, Darmstadt, Germany). Poly(vinyl alcohol) (PVA) granules with an average molecular weight (Mw) of 12.4 × 10⁴ g/mol and a 99–100% degree of hydrolysis and Glycerol (Gly) (99.6%) were purchased from Acros. Organics (Geel, Belgium). Copper chloride (II) dihydrate pure p.a. (CuCl₂·2H₂O) was purchased from Chempur (GmbH Rueppurrer, Karlsruhe, Germany); hydrochloric acid (HCl) ≥ 37% was purchased from Fluka (Honeywell Specialty Chemicals, Seelze, Germany); ethanol absolute (EtOH), 99.3%, toluene, and n-hexane were purchased from Chemical Company; and ammonium hydroxide solution (28–30%) was purchased from analysis EMSURE ACS. Reag. Ph Eur. Supelco. All reagent-containing inhibitors were passed through aluminium oxide to remove the stabilizer before usage. All the aqueous solutions were prepared in freshly distilled water.

Gelatin (20 g) was dissolved in distilled dimethyl sulfoxide (DMSO) at 50 °C. After the solution was fully mixed, 4-dimethylaminopyridine (2 g, Sigma Aldrich) and 4-methoxyphenol (0.2 g, Sigma Aldrich) were added in the DMSO solution (200 mL) at 50 °C. Glycidyl methacrylate (8 mL, Sigma Aldrich) was very slowly added to the mixed solution and the reaction was maintained for 2 d at 50 °C under dry nitrogen atmosphere. The mixed solution was dialyzed completely against deionized water and lyophilized to get GelMa. The chemical structure of GelMa was analyzed using ¹H NMR spectroscopy (400-MR DD2, Agilent) (Fig. S1).

We obtained the E. lata secondary metabolites eutypine, eutypinol, siccayne and eulatinol by fermentation of Eutypa lata, strain IBWF E16121 in 20 liters of BAF medium as described in Guan et al. (2020) [20 (link)]. We dissolved the fungal metabolites in 100% methanol to a stock of 10 mM, diluting to a working concentration of 10 μM, if not specified otherwise. The chemical homologues of the fungal metabolites, 4-HBAL (4-hydroxybenzyl aldehyde), 4-HBA (4-hydroxybenzyl alcohol), 4-methoxyphenol and hydroquinone were all purchased from Sigma-Aldrich (Merck, Darmstadt, Germany) and prepared in 2% methanol to stocks of 10 mM stocks and used at a final concentration of 50 μM, if not stated otherwise.

Itaconic acid (99%) was purchased from ECEM (Amsterdam, The Netherlands). 1,3-Propanediol (purum) was received from DuPont Tate&Lyle (Loudon, TN, USA). 1,6-hexanediol (97%) was purchased from Dr. Lobinger Chemie (Seesen, Germany). 1,4-Butanediol (99%) and methanesulfonic acid (99%) were obtained from Carl Roth (Karlsruhe, Germany). Butylated hydroxytoluene (BHT, 99%) and 4-methoxyphenol (MeHQ, 98%), titanium butoxide (97%) and zinc acetate dihydrate (99%) were obtained from Sigma Aldrich (St. Louis, MO, USA). All reagents were used without further purification.