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5 protocols using deuterated acetone

1

Synthesis of Methacrylate Polymer Precursors

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Methyl
methacrylate (MMA, 99%), ethyl methacrylate
(EMA, 99%), n-butyl methacrylate (BMA, 99%), n-hexyl methacrylate (HMA, 99%), DMAEMA (99%), and MAA (99.5%)
were purchased from Sigma-Aldrich (Gillingham, U.K.) and were passed
through a basic alumina column to remove inhibitor prior to polymerization.
2-Ethylhexyl methacrylate (EHMA, 98%) was purchased from Alfa Aesar
(Heysham, U.K.), and its inhibitor was removed using an alumina column.
Isopropanol (IPA, 99.9%), triethanolamine (TEA, 99%), 4,4′-azobis(4-cyanovaleric
acid) (ACVA), 1,4-dioxane (99.5%), trimethylsilyldiazomethane solution
(2.0 M in diethyl ether), benzyl bromide (BzBr, 98%), and deuterated
acetone were purchased from Sigma-Aldrich. Deuterated chloroform (CDCl3) and deuterated dimethyl sulfoxide (DMSO-d6) for NMR spectroscopy measurements were purchased from
VWR (Lutterworth, U.K.). Deionized water was obtained using an Elgastat
Option 3A water purifier (Elga, High Wycombe, U.K.). 4-Cyano-4-(2-phenylethanesulfanylthiocarbonyl)sulfanylpentanoic
acid (PETTC) used for RAFT polymerization was prepared and purified
in-house, as reported previously.35 (link) Unless
stated otherwise, all materials were used as received.
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2

Comprehensive Chemical Synthesis Protocol

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Urea (CH4N2O, Proquimsa, Coahuila, Mexico), phosphorus pentoxide (P2O5, Sigma-Aldrich, St. Louis, MO, USA), zinc powder (Chemical Dynamics, Florida, USA), ethanol (C2H6O, Sigma-Aldrich, St. Louis, MO, USA), methanol (CH4O, Sigma-Aldrich, St. Louis, MO, USA), acetone (C3H6O, Sigma-Aldrich, St. Louis, MO, USA), Toluene (C7H8, Sigma-Aldrich, St. Louis, MO, USA), Hexane (Sigma-Aldrich, St. Louis, MO, USA), Phosphoric Acid (H3PO4, Fermont, Nuevo León, Mexico), Ammonium Hydroxide 30% (NH4OH, Fermont, Nuevo León, Mexico), Hydrochloric Acid 30% (HCl, Fermont, Nuevo León, Mexico), porcine hematin (Sigma-Aldrich, St. Louis, MO, USA), aniline (Sigma-Aldrich, St. Louis, MO, USA), sodium carbonate (Na2CO3, Sigma-Aldrich, St. Louis, MO, USA), sodium bicarbonate (NaHCO3, Sigma-Aldrich St. Louis, MO, USA), p-toluene sulfonic acid (TSA, Sigma-Aldrich, St. Louis, MO, USA), hydrogen peroxide (H2O2, Sigma-Aldrich, St. Louis, MO, USA), Dimethyl sulfoxide (DMSO, Sigma-Aldrich, St. Louis, MO, USA), N-Methyl-2-pyrrolidone (NMP, Sigma-Aldrich, St. Louis, MO, USA), deuterated sulfuric acid (D2SO4, Sigma-Aldrich, St. Louis, MO, USA), deuterated DMSO (Sigma-Aldrich, St. Louis, MO, USA), deuterated acetone (Sigma-Aldrich, St. Louis, MO, USA) and deuterated water (D2O, Sigma-Aldrich, St. Louis, MO, USA).
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3

Enzymatic Esterification Optimization

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Sebacic acid (99.0%, Sigma-Aldrich),
lipase acrylic resin—CALB (lipase B from C.
antarctica
, ≥5000 U g–1,
Sigma-Aldrich), and deuterated acetone (99.9% atom D, Sigma-Aldrich)
were used without any treatment. Molecular sieves, 5 Å (spheres,
4–8 mesh, Sigma-Aldrich), were exhaustively washed with distilled
water and dried in an oven at 400 °C for 4 h. Glycerol (≥99.5%,
Sigma-Aldrich), tert-butanol (99.5%, Acros Organics),
acetone (≥99.5%, LabSynth), and acetonitrile (≥99.5%,
LabSynth) were kept under Molecular sieves. Tetrahydrofuran (≥99.0%,
Vetec) was dried using metallic sodium and benzophenone under reflux
and argon flow; this was followed by distillation and storage in a
closed bottle with Molecular sieves.
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4

Synthesis of Hydroxyapatite Biomaterial

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In this research, sebacic acid (CAS no.111-20-6), deuterated acetone (99.9 atom % D, contains 0.03 % (v/v) TMS) (CAS no. 666-52-4) and Glycerol (CAS no. 56-81-5) from Aldrich®, NaCl from P.P.H “STANLAB” Sp.J. (CAS no. 7647-14-5) with 400–500 µm grain size and tetrahydrofuran (CAS no. 109-99-9) from POCH S.A. were used. For the synthesis of hydroxyapatite, ammonia water (25%) from “STANLAB” Sp.J. (CAS no. 1336-21-6), calcium acetate monohydrate (CAS no. 5743-23-0) and disodium hydrogen phosphate (CAS no. 755-79-4) from CHEMPUR were used.
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5

Synthesis of Ruthenium Polypyridyl Complexes

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All materials were used as received without
further purification. Pyridine was acquired from Mallinckrodt Chemicals,
ammonium hexafluorophosphate and deuterated acetone were purchased
from Aldrich, diethyl ether and acetonitrile were obtained from Fisher
Scientific, and 200 proof ethanol was purchased from Decon Laboratories.
The complexes [Ru(tpy)(Me2bpy)Cl](PF6),30 (link) [Ru(tpy)(biq)Cl](PF6),31 and [Ru(tpy)(bpy)(py)](PF6)2 (1)24 were prepared by literature
methods.
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