Neo400

All reagents were obtained from Sigma-Aldrich and Fisher Scientific unless otherwise specified. Hydrogel macromers were prepared as described previously^{64 (link)}. Briefly, for all polymers, sodium hyaluronate (HA, MW = 60 kDa, Lifecore Biomedical) was modified with tetrabutylammonium salt (HA-TBA). Ad-HA modification was performed through the reaction of 1-adamantane acetic acid (Ad) and (dimethylamino)pyridine (DMAP) and ditert-butyl decarbonate (Boc2O) for 20 h at 45°C in anhydrous dimethyl sulfoxide (DMSO). CD-HA modification was performed through the reaction of Mono-(6-(1,6-hexamethylenediamine)-6-deoxy)-β-Cyclodextrin (Crysdot) and benzotriazol-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate (BOP) for 3 h at RT in DMSO. AHA modification was performed through the reaction of acrylic anhydride at a pH 9–10 for 3 h at RT in DI water. All polymers were purified via dialysis, lyophilized and modification was confirmed using ¹H NMR (Bruker Neo 400). AD-HA, CD-HA, and AHA of 12%, 20%, and 92% modification by ¹H NMR, respectively, were used for all experiments (Supplementary Fig. 1, analysis performed in TopSpin and MestReNova).

The NMR spectra have been recorded on a Bruker NEO 400 instrument (Bruker BioSpin, Rheinstetten, Germany) operating at 400.1 and 100.6 MHz for ¹H and ¹³C nuclei using either a 5 mm multinuclear inverse detection z-gradient probe or a 5 mm four nuclei direct detection z-gradient probe (mainly for 1D ¹³C spectra). Chemical shifts are reported in δ units (ppm) and were referenced to the internal deuterated solvent (DMSO-d₆ reference at 2.51 ppm (¹H) and 39.4 (¹³C) and CDCl₃ reference at 7.26 ppm (¹H) and 77.0 ppm (¹³C)). The signals were assigned based on 2D NMR homo- and heteronuclear correlations, such as H,H-COSY, H,C-HSQC and H,C-HMBC, recorded using standard pulse sequences in the version with z-gradients, as delivered by Bruker with TopSpin 4.0 PL8 spectrometer control and processing software. IR spectra were recorded on a Shimadzu IRTracer-100 instrument (Shimadzu U.S.A. Manufacturing, Inc., Canby, OR, USA). Mass spectra were recorded on a Thermo Scientific ISQ LT instrument (Thermo Fisher Scientific Inc., Waltham, MA, USA). Elemental analyses (C, H) were conducted using a CE440 Elemental Analyzer (Exeter Analytical, Coventry, United Kingdom); the results were found to be in good agreement (±0.30%) with the calculated values. Melting points were measured on a KSPI melting-point meter and are uncorrected (A.KRÜSS Optronic, Hamburg, Germany).