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6 protocols using anhydrous oxalic acid

1

Synthesis of Deep Eutectic Solvents

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Choline chloride (99%), ethylene glycol (99.5%), anhydrous FeCl3 (99%), anhydrous AlCl3 (99%) and LaCl3·7H2O (99.99%) were purchased from Acros Organics (Geel, Belgium). ZnCl2 (98%) was purchased from Chemlab-Analytical (Zedelgem, Belgium). Ethanol (99.9%), PbCl2 (98%), mEthanol-d4 (99.8%), Aliquat 336 (A336, a mixture of quaternary ammonium chlorides, with 88.2–90.6% quaternary ammonium content) and anhydrous oxalic acid (99%) from Sigma-Aldrich (Diegem, Belgium). Cyanex® 923 (C923, a mixture of trialkylphosphine oxides), Cyanex® 272 (bis(2,4,4-trimethylpentyl)phosphinic acid) were obtained from Cytec Solvay Group (New Jersey, USA), TBP (tri-n-butyl phosphate) from Alfa Aesar (USA). The aliphatic and aromatic diluents Shell GTL GS190 (C10–C13 aliphatic hydrocarbon diluent) and Shellsol A150 (C9–C11 aromatic hydrocarbon diluent) were obtained from Shell (Rotterdam, The Netherlands), ammonia solution (25%), hydrochloric acid (37%) and lactic acid (88%) from VWR International (Leuven, Belgium). All the chemicals were used as received, without any further purification. Ultrapure water (18.2 MΩ cm) was obtained by a Merck Millipore (Overijse, Belgium) Reference A+ Milli-Q water purification system.
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2

Silica-Based Heavy Metal Adsorbents

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Methyltriethoxysilane (MTES, ≥99%, Sigma-Aldrich, Darmstadt, Germany), tetraethylorthosilicate (TEOS, 98%, Sigma-Aldrich, Darmstadt, Germany), (3-aminopropyl)trimethoxysilane (APTMS, ≥97%, Sigma-Aldrich, Darmstadt, Germany), N1-(3-trimethoxysilylpropyl)diethylenetriamine (AAAPTMS, technical grade, Sigma-Aldrich, Darmstadt, Germany), 1-[3-(trimethoxysilyl)propyl]urea (UPTMS, 97%, Sigma-Aldrich, Darmstadt, Germany) and Tris[3 -(trimethoxysilyl)propyl] isocyanurate (TTMSI, >95.0%, Fluorochem, Derbyshire, United Kingdom) were used as silica sources. Methanol (99.8%, VWR International, Alfragide, Portugal) and ethanol (EtOH, ≥99.8%, Fisher, Porto Salvo, Portugal), anhydrous oxalic acid (≥99%, Sigma-Aldrich, Darmstadt, Germany), ammonium hydroxide (25% NH3 in H2O, Sigma-Aldrich, Darmstadt, Germany) were used as solvents and catalysts for the sol-gel chemistry. Heavy metal solutions were prepared using copper(II) nitrate hemipentahydrate (p.a., Chem-Lab, Zedelgem, Belgium), lead(II) nitrate (≥99.0%, Sigma-Aldrich, Darmstadt, Germany), cadmium nitrate tetrahydrate (≥99.0%, Sigma-Aldrich, Darmstadt, Germany), nickel(II) nitrate hexahydrate (crystals, Sigma-Aldrich, Darmstadt, Germany). High purity water was used whenever needed. Nitric acid (65%, Fisher) was used to adjust the solutions pH.
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3

Synthesis of Silica-Polymer Composite Electrolytes

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Tetraethyl orthosilicate (TEOS, 98%, Acros Organics, Antwerpen, Belgium) and methyltriethoxysilane (MTES, 99%, Sigma-Aldrich, Darmstadt, Germany) were used as silica sources. Anhydrous oxalic acid (p.a., ≥99%, Sigma-Aldrich) and ammonium hydroxide (25% as NH3, PanReac, Barcelona, Spain) were used as sol–gel catalysts. Poly(vinyl alcohol) (PVA, Mw 72,000 Da, 85–89% hydrolysis, PanReac) was selected as the polymer and sodium perchlorate monohydrate (NaClO4·H2O, 85+% as NaClO4, Thermo Scientific Chemicals, Waltham, MA, USA) was used as sodium salt. Ethanol (EtOH, ≥99%, Valente e Ribeiro, Belas, Portugal) and high-purity water were used as solvents. All substances were used as received.
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4

Synthesis of Metal Acetylacetonate Compounds

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Zinc acetylacetonate (Zn(AcAc)2; ≥95.0%), cobalt acetylacetonate (Co(AcAc)2; ≥99.0%), nickel acetylacetonate (Ni(AcAc)2; ≥99.0%), copper acetylacetonate (Cu(A0cAc)2; ≥99.0%), oxalic acid anhydrous (≥99.9%), hexadecyltrimethylammonium bromide (CTAB; ≥99.9%), polyethylene glycol (PEG; 10 000), carbamazepine and ethanol (absolute) were all purchased from Sigma Aldrich and used as provided. Jacketed, fritted funnels were purchased from Chemglass Lifesciences and fitted with PTFE sheets (Zwanzer). Desiccant from a Drierite™ gas-drying unit (Sigma-Aldrich) was used as provided by the manufacturer but transferred to a smaller tube.
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5

Epoxidized Linseed Oil-Chitosan Composites

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Epoxidized linseed oil (ELO; average molar mass = 980 Da; average functionality = 5.5 epoxides per triglyceride, viscosity~870 cPs/25 °C) was supplied by Valtris Specialty Chemicals (Manchester, UK). Chitosan (CHI; low molecular weight = 50–190 kDa; 84% deacetylated), oxalic acid anhydrous (OA; ≥99.0%), citric acid monohydrate (CA; ≥99.0%), and ethanol (EtOH; absolute, ≥99.8%) were purchased from Sigma Aldrich (Saint-Quentin-Fallavier, France). All chemical compounds were used as received without any further purification.
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6

Clofazimine Solubility Enhancement Protocol

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Clofazimine (CAS registry number 2030-63-9)
was purchased from Beijing Mesochem Technology Co., Ltd. Coformers,
including hydrochloric acid (37%, Sigma-Aldrich), sulfuric acid (95–97%,
Sigma-Aldrich), nitric acid (70%, Sigma-Aldrich), oxalic acid anhydrous
(>99%, Sigma-Aldrich), ortho-phosphoric acid (85%,
Sigma-Aldrich), citric acid monohydrate (>99%, Sigma-Aldrich),
formic
acid (acetic acid (>95%, Sigma-Aldrich)), and acetic acid (99.8%,
Sigma-Aldrich) were used as received. Methanol (>99%) being of
HPLC
grade and used without further purification was also purchased from
Sigma-Aldrich. Ingredients for the dissolution media; pepsin (extracted
from porcine mucosa, Amresco), sodium taurocholate hydrate (NaTc,
>97%, Sigma-Aldrich), L-α-phosphatidylcholine (lecithin,

99% purity, from bovine brain, Sigma-Aldrich), sodium chloride (Fisher
Scientific), maleic acid (>99%, Sigma-Aldrich), and hydrochloric
acid
(37%, Sigma-Aldrich) were used as received from suppliers. Brain Heart
Infusion Broth (Sigma-Aldrich) was used as a medium for bioactivity
assays.
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