Dmx 500

The mAGP preparation was subjected to base saponification to remove mycolic acids using 2% potassium hydroxide in methanol-toluene (1:1) for 48 h. The insoluble residue was recovered by centrifugation at 27,000 g. The sample was washed repeatedly with methanol and the resulting AGP treated with 75 ml of 2 M sodium hydroxide for 16 h at 80 °C. The supernatant, which contained base-solubilised AG, was recovered by centrifugation at 27,000 g for 30 min. The crude AG preparation was neutralised with acetic acid and dialysed to remove residual salts (MWCO 3500). The supernatant was diluted in cold ethanol (80%, v/v) and left at −20 °C overnight to precipitate the base-solubilised AG, which was then recovered by centrifugation and lyophilised. Nuclear magnetic resonance (NMR) spectra of samples were recorded using Bruker DMX-500. Samples were repeatedly exchanged in deuterium oxide (99.9 atom% D) with intermediate lyophilisation and analysed at 313 K. The ¹H and ¹³C NMR chemical shifts were referenced relative to internal acetone at 2.225 and 34.00 ppm, respectively. Details concerning NMR sequences used and experimental procedures were described previously (Daffé et al., 1990 (link)).

Food-grade Cinnamon oil (W229202) with a purity ≥98% was purchased from Sigma-Aldrich. The non-ionic surfactant Levenol C-201 was kindly donated by KAO Chemicals. The surfactant Levenol C-201 has a glycereth chain with 17 cocate groups, resulting in a surfactant with a HLB number ~13. Olive oil (Borges brand) with an acid degree 0.4° was purchased from a local supermarket. Chitosan (419419) with >75% deacetylation degree and high molecular weight, M_W ≈ 3.1–3.75 × 10⁵ g/mol, anhydrous calcium chloride (C1016) with a granularity ≤7 mm and purity ≥93%, trisodium trimetaphosphate (TTP) (T5508) (M_W = 305.89 g/mol) with purity ≥95%, Brilliant Blue G as a hydrophilic dye and Sudan IV as a hydrophobic dye were provided by Sigma-Aldrich. Technical-grade sodium alginate (Alg) with a ratio of β-D-mannuronic acid: α-L-guluronic acid = 58.9:41.1, measured using nuclear magnetic resonance (DMX-500, 500 MHz, Bruker, Billerica, MA, USA), and M_n ≈ 668,000 and M_W ≈ 1,750,000, obtained using size-exclusion chromatography as described in a previous work [8 (link)], was purchased from Panreac.

Unless stated otherwise, all reagents and solvents were used without further purification. The syntheses of the hybrid organic–inorganic rotaxanes were carried out in Erlenmeyer Teflon FEP flasks supplied by Fisher. Column chromatography was carried out using Silica 60A (particle size 35–70 μm, Fisher, UK) as the stationary phase, and TLC was performed on precoated silica gel plates (0.25 mm thick, 60 F254, Merck, Germany) and observed under ultraviolet light. NMR spectra were recorded on Bruker AV 400 and Bruker DMX 500 instruments. Chemical shifts are reported in p.p.m. from low to high frequency and referenced to the residual solvent resonance. electrospray ionization mass spectrometry, matrix-assisted laser desorption ionization-time of flight spectrometry and microanalysis were carried out by the services at the University of Manchester. Details of the synthetic procedures are given in the Supplementary Methods.
Details of the physical characterization and DEER studies are also given in the Supplementary Methods.

Fer (100 μg of Fe/ml) and Fer (100 μg of Fe/ml) + SnF₂ (100 μg/ml) prepared in DI water were used for determining hydrodynamic diameter and zeta potential. The measurements were carried out using a Nano-ZS 90 (Malvern Instrument, Malvern, UK) at indicated time points. TEM was performed using a Tecnai T12 (FEI Tecnai) electron microscope at 100 kV. In brief, solutions of Fer and Fer + SnF₂ were prepared in 0.1 M sodium acetate buffer (pH 4.5) and incubated for 1 h. After that, 5 μl of the solution of Fer or Fer + SnF₂ was dropped onto a TEM grid, and the liquid was dried before microscopy was conducted. ¹H NMR spectroscopic data of CMD with or without SnF₂ were recorded using a Bruker DMX 500, equipped with a z-gradient amplifier and 5 mm DUAL (1H/13C) z-gradient probe head, in D₂O. UV-visible absorption spectra were recorded using a Genesys 150 UV − visible spectrophotometer (Thermo Scientific, Waltham, MA).