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6 protocols using p toluenesulfonic acid monohydrate ptsa

1

Synthesis of Functionalized Polyester Nanoparticles

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All the reagents and solvents were used as received. Tetrahydrofuran (THF) (p.a.), n-hexane (p.a.), diethyl ether (p.a.), dichlorometane (p.a.), acetonitrile (p.a.), acetone (p.a.), NaOH (>99%) and NaHCO3 (>99.0%) were obtained from Merck, Darmstadt, Germany. Sodium (+)-l-ascorbate (>98%) was obtained from Sigma, Darmstadt, Germany. Triphosgene (>99.0%), n-hexylamine (99%), propargylamine (98%), 3-bromo-propanamine hydrobromide, 1-Hydroxybenzotriazole (HOBt) hydrate (97%), Amberlyst® A21, and Boc-Lys(Boc)-OSu (97.0%) were obtained from Aldrich, St. Louis, MO, USA. 2,2-Bis(hydroxymethyl)propionic acid (Bis-MPA) (98%), 2,2-dimetoxypropane (98%), p-toluenesulfonic acid (PTSA) monohydrate (95.5%), Na2CO3 (>99.8%), Na2SO4 (anhydrous, >99.0%), THF (>99.9%, anhydrous), N,N-dimethylformamide (DMF) (anhydrous, 99.8%), trifluoroacetic acid (TFA) (99%), NaN3 (>99.5%), triethylamine (>99%), MSA (>99.5%), ammonia solution (2.0 M in ethanol), and anisole (99%) were obtained from Sigma-Aldrich, St. Louis, MO, USA. NaCl (Ph Eur), NaHSO4 (95%) were obtained from Fluka, Buchs, Switzerland. γ-benzyl-l-glutamate (BGlu) (>99%), 4-(4,6-Dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM) (99+%), CuSO4·5H2O (99+%), and ethylenediaminetetraacetic acid (EDTA) (99%) were obtained from Acros Organics, Geel, Belgium. EDC (>98.0%) was obtained from TCI, Zwijndrecht, Belgium.
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2

Synthesis and Characterization of Polyurethane Materials

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5-hydroxymethyl furfural (HMF, AK Scientific, 98%), Pentaerythritol (Sigma-Aldrich, 99%), p-toluenesulfonic acid (p-TSA) monohydrate (Sigma-Aldrich, ≥98.5%), NaHCO3 (Sigma-Aldrich, ≥99.7%), Bismaleimide (Sigma-Aldrich, 95%), Ethylene glycol (EG, Sigma-Aldrich, anhydrous, 99.8%), ,4’-methylenebis(phenyl isocyanate) (MDI, Sigma-Aldrich, 98%), Isopropanol (Sigma-Aldrich, for HPLC), 4Acetone (Fisher Scientific, HPLC grade), Tetrahydrofuran (THF, Sigma-Aldrich, 250 ppm BHT inhibitor, ≥99.0%), Dimethyl sulfoxide (DMSO, Sigma-Aldrich, anhydrous, ≥99.9%), 4-methyl-2-pentanone (MIBK, Sigma-Aldrich, HPLC grade), Ethyl acetate (EtOAc, Sigma-Aldrich, for HPLC, ≥99.7%), Acetic acid (Sigma-Aldrich, ≥99.7%), Hydrochloric acid (HCl, 6 N, Fisher Scientific), Sodium acetate (NaOAc, Sigma-Aldrich, >99%), Mill-Q water (MQ water, ~18 MΩ cm), Acetone-d6 (ACROS organic, 99.8 atom% D, 0.03 % (v/v) TMS), Methanol-d4 (ACROS organic, 99.8 atom% D, 0.03 % (v/v) TMS), DMSO-d6 (Sigma-Aldrich, 99.9 atom% D, 0.03 % (v/v) TMS).
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3

Synthesis of Nitrophenyl-Substituted Triarylamine

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1,4-Dibromobenzene, 4-bromo-N,N-bis(trimethylsilyl)aniline, p-toluenesulfonic acid monohydrate (PTSA), n-butyllithium, anhydrous N,N-dimethylacetamide (DMAc), anhydrous calcium sulfate were purchased from Sigma-Aldrich (Milwaukee, WI, USA). 3-Nitrophenylboronic acid, 4-aminophenylboronic acid pinacol ester, bis(4-formylphenyl)phenylamine (TPA) and tetrabutylammonium hexafluorophosphate (TBAHFP) were obtained from AK Scientific, Inc. (San Francisco, USA). Potassium carbonate, chloroform, n-hexane, toluene, 1,4-dioxane, dichloromethane and tetrahydrofuran were purchased from Merck (Darmstadt, Germany). Except for THF, which was dried over sodium using benzophenone as indicator under nitrogen atmosphere and distilled immediately before its use, all reagents and solvents were used as received without further purification.
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4

Humins Polymerization under Acidic Conditions

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Humins were supplied by Avantium N.V. and produced in their pilot plant in Geleen, The Netherlands, by conversion of fructose and glucose. Humins samples were used as received. P-Toluenesulfonic acid monohydrate (pTSA) was supplied by Sigma Aldrich, (Mw = 190.22 g/mol, melting point = 103–106 °C, purity > 98.5%). PTSA was chosen as a catalyst to study humins polymerization under acidic conditions. For this purpose, a sample was prepared by heating humins for 20 min at 80 °C and then 1.5 wt % of pTSA was added. The mixture was stirred for another 20 min at 80 °C to obtain a homogenous sample.
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5

Ethanediol-Citric Acid Condensation

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Commercially available ethanediol (Fisher Chemical, >99%), anhydrous citric acid (Acros Organics, ≥99.5%), and p-toluenesulfonic acid monohydrate—PTSA (Sigma Aldrich, ≥98.5%) were used without prior preparation.
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6

Synthesis of Poly(ε-caprolactone) Derivatives

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Poly(ε-caprolactone) (PCL, CAPA 6500, Mw = 50,000) in the form of 3 mm pellets was obtained from Perstorp Caprolactones (Cheshire, UK) and used as received. l-leucine (≥98%), p-toluenesulfonic acid monohydrate (p-TSA) were purchased from Sigma-Aldrich (St. Louis, MO, USA). Anhydrous sodium carbonate (Na2CO3) was purchased from Fisher Chemical (Loughborough, UK). Triphosgene was obtained from TCI Europe (Zwijndrecht, Belgium), and 1,6-hexanediol (99%) were purchased from Acros Organics (Geel, Belgium). Chloroform (CHCl3), and toluene were supplied by José Manuel Gomes dos Santos Lda (Odivelas, Portugal). CHCl3 was dried over calcium chloride and distilled prior use. Deuterated dimethylsulfoxide (DMSO-d6) was purchased from Eurisotop (Saint-Aubin, France).
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