Aanalyst 100 system

All reagents and deuterated solvents used for synthesis were of reagent grade or better and were used without further purification unless stated otherwise. Starting materials, reagents and deuterated solvents were purchased from Sigma Aldrich, and all other solvents were purchased from Caledon Laboratories. The PNH₂ precursor, 5-(4-aminophenyl)-10, 15, 20-(tri-4-sulfonatophenyl)porphyrin triammonium, was purchased from PorphyChem. All reactions were carried out under argon. Thin layer chromatography was carried out on pre-coated aluminum plates of Silica Gel 60 F254 from Merck. Column chromatography was performed using Caledon Silica Gel 60. Dialysis was performed with Biotech CE dialysis tubing (MWCO 100–500 Da). Cation exchange was performed using an Aberlite IR120 H resin. All spectroscopic data for structural characterizations were obtained using the research facilities in the Department of Chemistry. NMR spectra were recorded on a Brucker-500 MHz. UV-visible spectra were recorded on an Agilent 8453 system. HPLC spectra were recorded on a PerkinElmer SERIES 200 system. FAA spectra were recorded on a PerkinElmer AAnalyst 100 system. Mass spectroscopy was carried out on a Agilent 6538 Q-TOF system.

The degree of conjugation was determined by a Bruker Autoflex Speed matrix-assisted laser desorption ionization time-of-flight mass spectrometer (MALDI-TOF/MS) at the University of Toronto Department of Chemistry AIMS Mass Spectrometry Laboratory (Supplementary Figures S30 and S31). MnTPPS₄ was used as a control for non-covalent absorption to HSA. Concentration and confirmation that free MnTPPS₃ was removed was determined with a AAnalyst 100 system (PerkinElmer, Waltham, MA, USA) with a Manganese Lumina Hollow Cathode Lamp at the University of Toronto Department of Chemistry ANALEST facility. (MnTPPS₃)_3.5HSA was found to have a purity of 99.0% while (MnTPPS₃)₆HSA had a purity of 97.4%.