For hydrogels without mineralization, an [Fe3+]:[catechol] ratio of 3:3 (“3:3” gels) and 1:3 (“1:3” gels) were used by mixing an appropriate volume of 0.2 M FeCl3 ∙ 6H2O (aq) with a 200 mg/mL 4cPEG solution (12.5 μL), then raising pH up to ~12 via mixing 4 M NaOH (aq) to produce 20 μL hydrogels of 125 mg/mL polymer concentration. The final concentrations of Fe3+ were 50 mM for the 3:3 gels and 16.67 mM for the 1:3 gels. The final concentrations of NaOH were 180 mM for the 3:3 gels and 100 mM for the 1:3 gels. Unless specified otherwise, the 3:3 gels are the reference sample without mineralization, which is labeled as “Mineral-Free” or “In Situ × 0” gels according to context.
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