Supporting Information. Sustainable Cotton Dyeing in Non-Aqueous Medium Applying Protic Ionic Liquids

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Supporting Information

Sustainable Cotton Dyeing in Non-Aqueous Medium Applying Protic Ionic Liquids Rebecca S. Andrade*,1,2, Dayse Torres3, Fábia R. Ribeiro4,Bruna G.

Chiari-Andréo5.6,João Augusto Oshiro Junior6 and Miguel Iglesias1 1

Departamento de Engenharia Química, Universidade Federal da Bahia, Rua Aristides Novis, 2, Federação. 40210-630 Salvador, Brasil

2

Centro de Ciência e Tecnologia em Energia e Sustentabilidade, Universidade Federal do Recôncavo da Bahia, Avenida Centenário, 697, Sim, 44042-280 Feira de Santana, Brasil

3

Departamento de Engenharia Têxtil, Universidade Estadual de Maringá, Avenida Reitor Zeferino Vaz, S/N, Centro, 87360-000 Goioere, Brasil

4

Campus Apucarana, Universidade Tecnológica Federal do Paraná, Rua Marcílio Dias, 635, Jardim Paraíso, 86812-460 Apucarana, Brasil

5

Universidade de Araraquara, UNIARA, Rua Carlos Gomes, 1338, Centro, 14801-340 Araraquara, Brasil.

6

Universidade Estadual Paulista (UNESP), Faculdade de Ciências Farmacêuticas, Rodovia Araraquara, Km 1, 14800-903 Araraquara, Brasil

*To whom correspondence should be addressed. Email: [email protected]

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Identification of 2-hydroxy ethylammonium acetate (2-HEAA)

The structure of 2-hydroxy ethylammonium acetate (2-HEAA) was identified by Nuclear Magnetic Resonance (NMR) and Fourier Transform Infrared (FT-IR) spectroscopies.

Figure S1. The numbering scheme of molecular structure of 2-hydroxy ethylammonium acetate (2-HEAA)

a) NMR spectrum

5 4 3 2 1

Chemical Shift (ppm)

Figure S2. The 1H-NMR spectrum of 2-hydroxy ethylammonium acetate (2-HEAA)

Table S1. The full assignments of the proton peaks of 2-hydroxy ethylammonium acetate (2-HEAA)

Proton number Proton kind 1H peak

1 Primary 1.611, s

2 Secondary 2.827-2.809, t

3 Secondary 3.513-3.497, t

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S3 b) FT-IR spectrum 4500 4000 3500 3000 2500 2000 1500 1000 500 0 A b s o rb a n c e ( % ) Wavenumber (cm-1) COO -C-H and NH+₃

Figure S3. The FT-IR spectrum of 2-hydroxy ethylammonium acetate (2-HEAA)

Identification of 2-hydroxy diethylammonium acetate (2-HDEAA)

The structure of 2-hydroxy diethylammonium acetate (2-HDEAA) was identified by Nuclear Magnetic Resonance (NMR) and Fourier Transform Infrared (FT-IR) spectroscopies.

Figure S4. The numbering scheme of molecular structure of 2-hydroxy diethylammonium acetate (2-HDEAA)

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a) NMR spectrum

5 4 3 2 1

Figure S5. The 1H-NMR spectrum of 2-hydroxy diethylammonium acetate (2-HDEAA)

Table S2. The full assignments of the proton peaks of 2-hydroxy diethylammonium acetate (2-HDEAA) Proton number Proton kind 1H peak

1 Primary 1.660, s

2, 2’ Secondary 3.599-3.617, t 3, 3’ Secondary 2.987-2.969, t

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S5 b) FT-IR spectrum 4500 4000 3500 3000 2500 2000 1500 1000 500 0 C-H and NH₃+ Wavenumbers (cm-1) COO -0 2 4 6 8 10 A b s o rb a n c e ( % )

Figure S6. The FT-IR spectrum of 2-hydroxy diethylammonium acetate (2-HDEAA)

Identification of 2-hydroxy ethylammonium Proprionate (2-HEAPr)

The structure of 2-hydroxy ethylammonium propionate (2-HEAPr) was identified by Nuclear Magnetic Resonance (NMR) and Fourier Transform Infrared (FT-IR) spectroscopies.

Figure S7. The numbering scheme of molecular structure of 2-hydroxy ethylammonium propionate (2-HEAPr)

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a) NMR spectrum

5 4 3 2 1

C h e m ica l S h ift (p p m )

Figure S8. The 1H-NMR spectrum of 2-hydroxy ethylammonium propionate (2-HEAPr) Table S3. The full assignments of the proton peaks of 2-hydroxy ethylammonium propionate

(2-HEAPr)

Proton number Proton kind 1H peak

1 Secondary 1.897-1.859, d

2 Primary 0.764-0.739, t

3 Secondary 3.519-3.501, t 4 Secondary 2.837-2.819, t

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S7 b) FT-IR spectrum 4500 4000 3500 3000 2500 2000 1500 1000 500 0 A b s o rb a n c e ( % ) Wavenumber(cm-1) COO -C-H and NH+₃

Figure S9. The FT-IR spectrum of 2-hydroxy ethylammonium propionate (2-HEAPr)

Identification of 2-hydroxy ethylammonium Lactate (2-HEAL)

The structure of 2-hydroxy ethylammonium Lactate (2-HEAL) was identified by Nuclear Magnetic Resonance (NMR) and Fourier Transform Infrared (FT-IR) spectroscopies.

Figure S10. The numbering scheme of molecular structure of 2-hydroxy ethylammonium Lactate (2-HEAL)

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a) NMR spectrum

5 4 3 2 1

Figure S11. The 1H-NMR spectrum of 2-hydroxy ethylammonium Lactate (2-HEAL)

Table S4. The full assignments of the proton peaks of (2-HEAL) Proton number Proton kind 1H peak

1 Secondary 3.989-3.954, d 2 Primary 1.193-1.181, t 3 Secondary 3.684-3.667, d 4 Secondary 3.006-2.988, t - Solvent (DHO) 4.700, s b) FT-IR spectrum

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S9 4500 4000 3500 3000 2500 2000 1500 1000 500 0 C-H and NH+₂ A b s o rb a n c e (% ) Wavenumber (cm-1)

COO-Figure S12. The FT-IR spectrum of 2-hydroxy ethylammonium Lactate (2-HEAL)

Identification of 2-hydroxy diethylammonium lactate (2-HDEAL)

The structure of 2-hydroxy diethylammonium lactate (2-HDEAL) was identified by Nuclear Magnetic Resonance (NMR) and Fourier Transform Infrared (FT-IR) spectroscopies.

Figure S13. The numbering scheme of molecular structure of 2-hydroxy diethylammonium lactate (2-HDEAL)

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5 4 3 2 1

Figure S14. The 1H-NMR spectrum of 2-hydroxy diethylammonium lactate (2-HDEAL)

Table S5. The full assignments of the proton peaks of 2-hydroxy diethylammonium lactate (2-HDEAL) Proton number Proton kind 1H peak

1 Secondary 3.990-4.025, s 2 Primary 1.188-1.176, t 3,3’ Secondary 3.713-3.695, s 4,4’ Secondary 3.088-3.071, t - Solvent (DHO) 4.700, s b) FT-IR spectrum 4500 4000 3500 3000 2500 2000 1500 1000 500 0 C-H and NH+₃ A b s o rb a n c e ( % ) Wavenumber(cm-1)

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Identification of 2-hydroxy diethylammonium propionate (2-HDEAPr)

The structure of 2-hydroxy diethylammonium propionate (2-HDEAPr) was identified by Nuclear Magnetic Resonance (NMR) and Fourier Transform Infrared (FT-IR) spectroscopies.

Figure S16. The numbering scheme of molecular structure of 2-hydroxy diethylammonium propionate (2-HDEAPr)

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5 4 3 2 1

Figure S17. The 1H-NMR spectrum of 2-hydroxy diethylammonium propionate (2-HDEAPr)

Table S6. The full assignments of the proton peaks of 2-hydroxy diethylammonium propionate (2-HDEAPr)

Proton

number Proton kind

1 H peak 1 Secondary 1.9223-1.9605, m 2 Primary 0.8051-0.8299, t 3,3’ Secondary 3.6194-3.6374, t 4,4’ Secondary 2.9870-3.0043, t - Solvent (DHO) 4.7000, s

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S13 b) FT-IR spectrum 4500 4000 3500 3000 2500 2000 1500 1000 500 0 A b s o rb a n c e ( % ) Wavenumber (cm-1) COO -C-H and NH+₂

Figure S18. The FT-IR spectrum of 2-hydroxy diethylammonium propionate (2-HDEAPr)

Identification of 2-hydroxy diethylammonium succinate (2-HDEASu)

The structure of 2-hydroxy diethylammonium succinate (2-HDEASu) was identified by Nuclear Magnetic Resonance (NMR) and Fourier Transform Infrared (FT-IR) spectroscopies.

Figure S19. The numbering scheme of molecular structure of 2-hydroxy diethylammonium succinate (2-HDEASu)

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a) NMR spectrum

5 4 3 2 1

Figure S20. The 1H-NMR spectrum of 2-hydroxy diethylammonium succinate (2-HDEASu)

Table S7. The full assignments of the proton peaks of 2-hydroxy diethylammonium succinate (2-HDEASu)

Proton

number Proton kind

1 H peak 1,1’ Secondary 2.2140,s 2,2’ Secondary 3.6679-3.6854, t 3,3’ Secondary 3.0413-3.0589, t - Solvent (DHO) 4.7008, s

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Figure S21. The FT-IR spectrum of 2-hydroxy diethylammonium succinate (2-HDEASu)

Identification of 2-hydroxy diethylammonium formate (2-HDEAF)

The structure of 2-hydroxy diethylammonium formate (2-HDEAF) was identified by Nuclear Magnetic Resonance (NMR) and Fourier Transform Infrared (FT-IR) spectroscopies.

Figure S22. The numbering scheme of molecular structure of 2-hydroxy diethylammonium formate (2-HDEAF)

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a) NMR spectrum

Figure S23. The 1H-NMR spectrum of 2-hydroxy diethylammonium formate (2-HDEAF)

Table S8. The full assignments of the proton peaks of 2-hydroxy diethylammonium formate (2-HDEAF)

Proton

number Proton kind

1 H peak 1 Primary 8.342, s 2,2’ Secondary 3.0600, t 3,3’ Secondary 3.7000, t - Solvent (DHO) 4.7000, s

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Figure S24. The FT-IR spectrum of 2-hydroxy diethylammonium formate (2-HDEAF)

Identification of 2-hydroxy diethylammonium maleate (2-HDEAMa)

The structure of 2-hydroxy diethylammonium maleate (2-HDEAMa) was identified by Nuclear Magnetic Resonance (NMR) and Fourier Transform Infrared (FT-IR) spectroscopies.

Figure S25. The numbering scheme of molecular structure of 2-hydroxy diethylammonium maleate (2-HDEAMa)

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a) NMR spectrum

5 4 3 2 1

Figure S26. The 1H-NMR spectrum of 2-hydroxy diethylammonium maleate (2-HDEAMa)

Table S9. The full assignments of the proton peaks of 2-hydroxy diethylammonium maleate (2-HDEAMa)

Proton

number Proton kind

1 H peak 1,1’ Secondary 6.3854,s 2,2’ Secondary 3.7250-3.7425, t 3,3’ Secondary 3.0974-3.1148, t - Solvent (DHO) 4.6985,s

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S19 b) FT-IR spectrum 4500 4000 3500 3000 2500 2000 1500 1000 500 0 A b s o rb a n c e ( % ) Wavenumber (cm-1) C-H and NH+₂ COO

-Figure S27. The FT-IR spectrum of 2-hydroxy diethylammonium maleate (2-HDEAMa)

Identification of 2-hydroxy diethylammonium oxalate (2-HDEAOx)

The structure of 2-hydroxy diethylammonium oxalate (2-HDEAOx) was identified by Nuclear Magnetic Resonance (NMR) and Fourier Transform Infrared (FT-IR) spectroscopies.

Figure S28. The numbering scheme of molecular structure of 2-hydroxy diethylammonium oxalate (2-HDEAOx)

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a) NMR spectrum

5 4 3 2 1

Figure S29. The 1H-NMR spectrum of 2-hydroxy diethylammonium oxalate (2-HDEAOx)

Table S10. The full assignments of the proton peaks of 2-hydroxy diethylammonium oxalate (2-HDEAOx)

Proton

number Proton kind

1

H peak 1,1’ Secondary 3.7098-3.7285, t 2,2’ Secondary 3.0855-3.1029, t

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S21 b) FT-IR spectrum 4500 4000 3500 3000 2500 2000 1500 1000 500 0 A b s o rb a n c e ( % ) Wavenumber (cm-1) COO -C-H and NH+₂

Figure S30. The FT-IR spectrum of 2-hydroxy diethylammonium oxalate (2-HDEAOx)

Identification of 2-hydroxy diethylammonium salicylate (2-HDEASa)

The structure of 2-hydroxy diethylammonium salicylate (2-HDEASa) was identified by Nuclear Magnetic Resonance (NMR) and Fourier Transform Infrared (FT-IR) spectroscopies.

Figure S31. The numbering scheme of molecular structure of 2-hydroxy diethylammonium salicylate (2-HDEASa)

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a) NMR spectrum

5 4 3 2 1

Figure S32. The 1H-NMR spectrum of 2-hydroxy diethylammonium salicylate (2-HDEASa)

Table S11. The full assignments of the proton peaks of 2-hydroxy diethylammonium salicylate (2-HDEASa)

Proton

number Proton kind

1 H peak 1 Secondary 7.6113 – 7,6249, d 2 Secondary 7.1829-7.2083, t 3 Secondary 6.6973-6.7400, m 4,4’ Secondary 3.6218-3.6396, t 5,5’ Secondary 2.9483-2.9662, t - Solvent (DHO) 4.7000, s

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S23 b) FT-IR spectrum 4500 4000 3500 3000 2500 2000 1500 1000 500 0 C-H and NH+ 2 A b s o rb a n c e ( % ) Wavenumber (cm-1) COO

-Figure S33. The FT-IR spectrum of 2-hydroxy diethylammonium salicylate (2-HDEASa)

Identification of 2-hydroxy ethylammonium adipate (2-HEAAd)

The structure of 2-hydroxy ethylammonium adipate (2-HEAAd) was identified by Nuclear Magnetic Resonance (NMR) and Fourier Transform Infrared (FT-IR) spectroscopies.

Figure S34. The numbering scheme of molecular structure 2-hydroxy ethylammonium adipate (2-HEAAd)

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a) NMR spectrum

5 4 3 2 1

Figure S35. The 1H-NMR spectrum of 2-hydroxy ethylammonium adipate (2-HEAAd)

Table S12. The full assignments of the proton peaks of 2-hydroxy ethylammonium adipate (2-HEAAd)

Proton

number Proton kind

1 H peak 1,1’ Secondary 1.9577, t 2,2’ Secondary 1.3119, m 3 Secondary 3.5541-3.5720, t 4 Secondary 2.8623-2.8808, t - Solvent (DHO) 4.7000, s

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S25 b) FT-IR spectrum 4500 4000 3500 3000 2500 2000 1500 1000 500 0 A b s o rb a n c e ( % ) Wavenumber (cm-1) COO -C-H and NH+₃

Figure S36. The FT-IR spectrum of 2-hydroxy ethylammonium adipate (2-HEAAd)

Identification of 2-hydroxy ethylammonium citrate (2-HEACi)

The structure of 2-hydroxy ethylammonium citrate (2-HEACi) was identified by Nuclear Magnetic Resonance (NMR) and Fourier Transform Infrared (FT-IR) spectroscopies.

Figure S37. The numbering scheme of molecular structure 2-hydroxy ethylammonium citrate (2-HEACi)

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a) NMR spectrum

5 4 3 2 1

Figure S38. The 1H-NMR spectrum of 2-hydroxy ethylammonium citrate (2-HEACi)

Table S13. The full assignments of the proton peaks of 2-hydroxy ethylammonium citrate (2-HEACi)

Proton

number Proton kind

1 H peak 1,1’ Secondary 2.3619-2.5015, m 2 Secondary 3.6330-3.6499, t 3 Secondary 2.9386-2.9556, t - Solvent (DHO) 4.6998, s

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S27 b) FT-IR spectrum 4500 4000 3500 3000 2500 2000 1500 1000 500 0 A b s o rb a n c e ( % ) Wavenumber (cm-1) COO -C-H and NH+₃

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Supplementary Table S14. Density (gcm-3), ultrasonic velocity (ms-1) and isentropic compressibility (TPa-1) for the studied protic ionic liquids at a range of temperature 293.15 – 318.15 K.

2-HDEAA 2-HDEAF 2-HDEAL

T / (K) ρ (gcm-3) u (ms-1) κS (TPa-1) ρ (gcm-3) u (ms-1) κS (TPa-1) ρ (gcm-3) u (ms-1) κS (TPa-1)

293.15 1.1705 1876.90 242.5193 1.1973 1811.20 254.6034 1.2229 1858.50 236.7467 298.15 1.1675 1863.35 246.6915 1.1940 1798.54 258.9140 1.2198 1840.75 241.9478 303.15 1.1644 1850.31 250.8469 1.1908 1786.27 263.1885 1.2168 1826.86 246.2466 308.15 1.1613 1837.52 255.0301 1.1875 1774.09 267.5562 1.2138 1814.70 250.1746 313.15 1.1583 1824.86 259.2506 1.1843 1761.87 272.0136 1.2111 1803.64 253.8168 318.15 1.1552 1812.16 263.6026 1.1810 1749.60 276.6130 1.2085 1793.12 257.3562

2-HDEAMa 2-HDEAOx 2-HDEAPr

293.15 1.2833 2133.42 171.2060 1.2637 2052.41 187.8572 1.1380 1746.75 288.0025 298.15 1.2808 2101.14 176.8515 1.2613 2044.39 189.6942 1.1348 1730.48 294.2710 303.15 1.2785 2077.31 181.2578 1.2588 2037.44 191.3699 1.1315 1715.13 300.4356 308.15 1.2762 2058.71 184.8804 1.2566 2031.38 192.8504 1.1282 1700.29 306.5970 313.15 1.2741 2043.86 187.8859 1.2544 2025.81 194.2525 1.1249 1685.81 312.8015 318.15 1.2722 2031.40 190.4819 1.2525 2020.66 195.5401 1.1216 1671.47 319.1279

2-HDEASa 2-HDEASu 2-HEAA

293.15 1.1981 1796.63 258.5768 1.2319 2021.01 198.7411 1.1512 1805.53 266.4648 298.15 1.1950 1788.52 261.6041 1.2293 2008.18 201.7144 1.1484 1790.94 271.4843 303.15 1.1919 1780.24 264.7299 1.2266 1997.45 204.3361 1.1455 1777.87 276.1881 308.15 1.1887 1771.76 267.9896 1.2242 1988.03 206.6816 1.1427 1765.73 280.6850 313.15 1.1856 1763.07 271.3455 1.2219 1979.36 208.8886 1.1399 1754.15 285.1017 318.15 1.1824 1754.17 274.8478 1.2199 1971.07 210.9948 1.1370 1742.90 289.5307

2-HEAAd 2-HEACi 2-HEAL

293.15 1.1964 2028.38 203.1538 1.3269 2135.84 165.2055 1.2164 1893.41 229.3159 298.15 1.1941 2013.74 206.5154 1.3245 2113.36 169.0445 1.2136 1877.02 233.8765 303.15 1.1919 2002.30 209.2675 1.3220 2096.48 172.1025 1.2109 1863.76 237.7452 308.15 1.1899 1993.10 211.5589 1.3194 2083.20 174.6472 1.2083 1852.31 241.2114 313.15 1.1880 1984.84 213.6646 1.3167 2072.38 176.8375 1.2058 1841.66 244.5152 318.15 1.1863 1977.51 215.560 1.3141 2063.64 178.6914 1.2038 1831.91 247.5354 2-HEAPr T / (K) ρ (gcm-3) u (ms-1) κS (TPa-1) 293.15 1.0958 1652.14 334.3297 298.15 1.0926 1636.90 341.5816 303.15 1.0893 1622.44 348.7508 308.15 1.0861 1608.57 355.8363 313.15 1.0828 1595.05 362.9971 318.15 1.0796 1581.78 370.2073