Anna Pierrard, Arthur Helsen, Mugdha Joglekar, Thibault Sampon, Hans Duimel, Louis Pitet, Stefan Giselbrecht, Dominik Schauenburg, Matthew Baker. “Progress towards biomimetic supramolecular hydrogels capable of dual covalent/dynamic covalent stabilization.” ChemRxiv (). https://doi.org/10.26434/chemrxiv.15007911/v1

PEG-DAD
GPC (chloroform) Apparent number-average molar mass (Mn) = 24,200 g/mol, mass-average molar mass (Mw) = 26,600 g/mol, z-average molar mass (Mz) = 29,750 g/mol, and polydispersity (Mw/Mn) = 1.1; image data were not transcribed
SI, p. 10
BTA-Ald hydrogelator
GPC (chloroform) Apparent number-average molar mass (Mn) = 22,000 g/mol, mass-average molar mass (Mw) = 26,100 g/mol, z-average molar mass (Mz) = 30,850 g/mol, and polydispersity (Mw/Mn) = 1.2; image data were not transcribed
Nile Red fluorescence spectroscopy (H₂O:MeOH 95:5 v/v) Emission intensity increased modestly with BTA-Ald concentration from 1 to 10 mg/mL; λmax = 632 nm at all BTA-Ald concentrations, compared with λmax = 652 nm for the PEG 20,000 g/mol reference solution; image data were not transcribed
TEM (10 mg/mL, H₂O:MeOH 95:5 v/v) Extended fibrous structures appeared as dense bundles at low magnification and entangled fibrillar aggregates at higher magnification; image data were not transcribed
CryoTEM (10 mg/mL, H₂O:MeOH 95:5 v/v) Clear nanoscale aggregates were observed in the vitrified hydrated state; image data were not transcribed
Main, p. 8; SI, pp. 15–16
BTA-Ald hydrogels
Vial inversion, apparent critical gelation concentration 7.5–6.0 wt%; image data were not transcribed
CryoSEM (10 wt%, non-heated) A fractured cross-section revealed a fibrous network with fibrillar features appearing to intersect the fracture plane; image data were not transcribed
CryoSEM (10 wt%, heated to 80 °C) A fractured cross-section revealed fibrillar features intersecting the fracture plane; a longitudinal fracture revealed aligned fibrillar features extending along the fracture plane; image data were not transcribed
Rheology, storage modulus G′ (10 wt%, non-heated) 250 ± 5 Pa
Rheology, storage modulus G′ (10 wt%, heated to 80 °C) 3,690 ± 60 Pa
Rheology, frequency sweeps (10 wt%, non-heated and heated to 80 °C) G′ exceeded G″ over the frequency range tested; image data were not transcribed
Rheology, flow sweeps (10 wt%, non-heated and heated to 80 °C) Both systems showed shear-thinning behavior; the heated hydrogel displayed higher viscosity over most of the shear-rate range; image data were not transcribed
Rheology, stress relaxation (10 wt%, non-heated and heated to 80 °C) The non-heated hydrogel showed substantial stress relaxation; the heated hydrogel relaxed more slowly and retained a larger fraction of its initial stress over the experimental timescale; image data were not transcribed
Rheology, time sweep (10 wt%, non-heated) G′ increased by approximately one order of magnitude over 17 h under the solvent trap; a roughly fivefold increase was observed within the first 8–10 h in the humidity chamber; image data were not transcribed
Main, pp. 9–13; SI, pp. 17–20
BTA-Ald hydrogelator and non-heated and heated BTA-Ald hydrogels
FTIR The BTA-Ald hydrogelator and non-heated hydrogel showed no significant changes; comparison of non-heated and heated hydrogels showed no clear spectral shift, including in the carbonyl region, and only slight broadening of the O–H band, which could not be unambiguously assigned; image data were not transcribed
Main, pp. 9, 11; SI, p. 14
O-benzylhydroxylamine-functionalized BTA-Ald hydrogels
Rheology, storage modulus G′ (10 wt%, non-heated) 2,870 ± 40 Pa
Rheology, storage modulus G′ (10 wt%, heated to 80 °C) 6,190 ± 80 Pa
Rheology, frequency sweeps (10 wt%, non-heated and heated to 80 °C) G′ remained higher than G″ over the measured range; image data were not transcribed
Rheology, flow sweeps (10 wt%) Shear-thinning behavior was observed; image data were not transcribed
Rheology, stress relaxation (10 wt%, non-heated and heated to 80 °C) The non-heated functionalized hydrogel relaxed more rapidly than the non-functionalized BTA-Ald hydrogel; the heated functionalized hydrogel showed a relaxation behavior distinct from the heated BTA-Ald network; image data were not transcribed
Main, p. 14; SI, p. 23
PBH- and ADH-crosslinked BTA-Ald hydrogels
Rheology, storage modulus G′ (10 wt%, PBH-crosslinked, non-heated) 3,000 ± 40 Pa
Rheology, storage modulus G′ (10 wt%, ADH-crosslinked, non-heated) 5,150 ± 60 Pa
Rheology, storage modulus G′ (10 wt%, PBH-crosslinked, heated to 80 °C) 3,070 ± 19 Pa
Rheology, storage modulus G′ (10 wt%, ADH-crosslinked, heated to 80 °C) 3,720 ± 20 Pa
Rheology, frequency sweeps (10 wt%, non-heated) G′ remained higher than G″ over the investigated frequency range for both dynamically crosslinked networks; image data were not transcribed
Rheology, flow sweeps (10 wt%) All dynamically crosslinked hydrogels retained shear-thinning behavior; image data were not transcribed
Main, pp. 15–16
BMA-Acetal, BDA-Acetal and BTA-Acetal
¹H and ¹³C NMR spectra Image data were not transcribed
SI, p. 8
BTE-F5Ph, PEG-CDI, PEG-DAD, BTA-Acetal and BTA-Ald
¹H NMR spectra Image data were not transcribed
SI, pp. 6, 10–11, 13–14
BTA-Oxime and BTA-Hydrazone
¹H NMR spectra (700 MHz, DMSO-d₆) Image data were not transcribed