Supporting Information Silica Surface Modification and its Application in Permanent Link with Nucleic Acids Krzysztof Kuciński, a Magdalena Jankowska-Wajda, a Tomasz Ratajczak, b Sandra Bałabańska-Trybuś, b Anna Schulmann, a Hieronim Maciejewski, a Marcin K. Chmielewski b and Grzegorz Hreczycho a,* a Faculty of Chemistry, Adam Mickiewicz University in Poznań, Umultowska 89b, 61-614 Poznań (Poland). b Institute of Bioorganic Chemistry, Polish Academy of Sciences, Noskowskiego 12/14, 61-704 Poznań (Poland). S1
Characterization Data of Products: 3-((2-Trimethylsiloxy)ethoxy)propylethoxydimethylsilane (Table 1, entry 1) was obtained as colourless oil (88%); 1 H NMR: (400 MHz, C 6 D 6 ): (ppm) = 0.07 (s, 6H), 0.13 (s, 9H), 0.56-0.66 (m, 2H), 1.10 (t, J = 7.0 Hz, 3H), 1.60-1.76 (m, 2H), 3.32 (t, J = 6.7 Hz, 2H), 3.43 (dd, J = 5.6, 4.9 Hz, 2H), 3.51 (q, J = 7.0 Hz, 2H), 3.65-3.76 (m, 2H). 13 C NMR: (101 MHz, C 6 D 6 ): (ppm) = -2.3, -0.6, 12.6, 18.5, 23.7, 57.9, 62.2, 72.2, 73.7. MS (EI) m/z (rel. int.): 249(80), 229 (10), 189 (50), 145 (100), 117 (70), 103 (80). EA: C 12 H 30 O 3 Si 2 (278.54): calcd. C, 51.75; H, 10.86; found C, 51.79; H, 10.79. 2-((4-Trimethylsiloxy)butoxy)ethylethoxydimethylsilane (Table 1, entry 2) was obtained as colourless oil (90%); 1 H NMR: (400 MHz, C 6 D 6 ): (ppm) = 0.09 (s, 9H), 0.12 (s, 6H), 1.02-1.08 (m, 2H), 1.11 (t, J = 7.0 Hz, 3H), 1.55-1.75 (m, 4H), 3.23-3.36 (m, 2H), 3.46-3.61 (m, 6H). 13 C NMR: (101 MHz, C 6 D 6 ): (ppm) = -1.7, -0.7, 18.2, 18.5, 26.5, 29.7, 57.9, 62.2, 67.0, 70.2. MS (EI) m/z (rel. int.): 250 (5), 219 (25), 176 (90), 163 (50), 149 (70), 103 (100), 75 (50). EA: C 13 H 32 O 3 Si 2 (292.19): calcd. C, 53.37; H, 11.03; found C, 53.52; H, 11.11. 2-((2-Trimethylsiloxy)ethoxy)ethylethoxydimethylsilane (Table 1, entry 3) was obtained as colourless oil (87%); 1 H NMR: (400 MHz, C 6 D 6 ): (ppm) = 0.10 (s, 6H), 0.12 (s, 9H), 0.92-1.20 (m, 5H), 3.35-3.43 (m, 2H), 3.46-3.57 (m, 4H), 3.62-3.71 (m, 2H). 13 C NMR: (101 MHz, C 6 D 6 ): (ppm) = -1.7, -0.6, 18.2, 18.4, 57.8, 62.1, 67.4, 71.9. MS (EI) m/z (rel. int.): 219 (20), 191 (100), 177 (90), 149 (30), 133 (20), 103 (90), 75 (20). EA: C 11 H 28 O 3 Si 2 (264.51): calcd. C, 49.95; H, 10.67; found C, 49.87; H, 10.75. 3-(2,2-Bis(trimethylsiloxymethyl)butoxy)propylethoxydimethylsilane (Table 1, entry 4) was obtained as colourless oil (85%); 1 H NMR: (400 MHz, C 6 D 6 ): (ppm) = 0.09 (s, 6H), 0.11 (s, 3H), 0.14 (s, 18H), 0.58-0.66 (m, 2H), 0.91-1.03 (m, 4H), 1.12 (t, J = 7.0 Hz, 3H), 1.58-1.70 (m, 2H), 3.36 (s, 2H), 3.51-3.55 (m, 2H), 3.61 (s, 4H). 13 C NMR: (101 MHz, C 6 D 6 ): (ppm) = -2.3, -0.8, 7.6, 12.5, 18.5, 22.0, 23.6, 44.1, 57.9, 62.2, 70.1, 74.0. MS (EI) m/z (rel. int.): 262 (5), 245 (10), 221 (15), 119 (50), 177 (90), 145 (60), 103 (100), 73 (63). EA: C 19 H 46 O 4 Si 3 (422.82): calcd. C, 53.97; H, 10.97; found C, 53.89; H, 10.95. 3-(2,3-Bis(trimethylsiloxy)propoxy)propylethoxydimethylsilane (Table 1, entry 5) was obtained as colourless oil (84%); 1 H NMR: (400 MHz, C 6 D 6 ): (ppm) = 0.08 (s, 6H), 0.12 (s, 9H), 0.22 (s, 9H), 0.56-0.66 (m, 2H), 1.11 (t, J = 7.0 Hz, 3H), 1.60-1.73 (m, 2H), 3.26-3.37 (m, 2H), 3.41-3.59 (m, 4H), 3.60-3.75 (m, 2H), 3.95-4.07 (m, 1H). 13 C NMR: (101 MHz, C 6 D 6 ): (ppm) = -2.3, -0.7, 0.2, 12.5, 18.5, 23.6, 57.9, 64.9, 72.9, 72.9, 73.9. MS (EI) m/z (rel. int.): 248 (10), 230 (20), 219 (40), 205 (40), 189 (60), 177 (25), 154 (30), 147 (100), 129 (40), 103 (90). EA: C 16 H 40 O 4 Si 3 (380.74): calcd. C, 50.47; H, 10.59; found C, 50.52; H, 10.88. 3-((2-Trimethylsiloxy)ethoxy)propyldiethoxymethylsilane (Table 1, entry 6) was obtained as colourless oil (86%); S2
1 H NMR: (400 MHz, C 6 D 6 ): (ppm) = 0.10 (s, 3H), 0.11 (s, 9H), 0.66-0.72 (m, 2H), 1.13 (t, J = 7.0 Hz, 6H), 1.68-1.77 (m, 2H), 3.28-3.44 (m, 4H), 3.62-3.71 (m, 6H). 13 C NMR: (101 MHz, C 6 D 6 ): (ppm) = -5.0, -0.6, 10.2, 18.3, 23.4, 57.7, 62.2, 72.2, 73.5. MS (EI) m/z (rel. int.): 234 (100), 219 (30), 19 (20), 127 (10), 92 (10). EA: C 13 H 32 O 4 Si 2 (308.56): calcd. C, 50.60; H, 10.45; found C, 50.68; H, 10.38. 2-((4-Trimethylsiloxy)butoxy)ethyldiethoxymethylsilane (Table 1, entry 7) was obtained as colourless oil (85%); 1 H NMR: (400 MHz, C 6 D 6 ): (ppm) = 0.09 (s, 9H), 0.16 (s, 3H), 1.09-1.20 (m, 8H), 1.61-1.69 (m, 4H), 3.26-3.37 (m, 2H), 3.48-3.53 (m, 2H), 3.55-3.61 (m, 2H), 3.67 (q, J = 7.0 Hz, 4H). 13 C NMR: (101 MHz, C 6 D 6 ): (ppm) = -4.1, -0.7, 16.2, 18.3, 26.5, 29.7, 57.8, 62.2, 66.7, 70.1. MS (EI) m/z (rel. int.): 249 (75), 207 (100), 176 (20), 163 (30), 145 (70), 133 (70), 102 (10). EA: C 14 H 34 O 4 Si 2 (322.20): calcd. C, 52.13; H, 10.62; found C, 52.29; H, 10.60. 2-((2-Trimethylsiloxy)ethoxy)ethyldiethoxymethylsilane (Table 1, entry 8) was obtained as colourless oil (87%); 1 H NMR: (400 MHz, C 6 D 6 ): (ppm) = 0.12 (s, 9H), 0.15 (s, 3H), 1.12 (t, J = 7.0 Hz, 6H), 1.15-1.19 (m, 2H), 3.41 (t, J = 5.2 Hz, 2H), 3.59-3.63 (m, 2H), 3.64-3.70 (m, 6H). 13 C NMR: (101 MHz, C 6 D 6 ): (ppm) = -4.2, -0.6, 16.3, 18.3, 57.8, 62.2, 67.1, 71.9. MS (EI) m/z (rel. int.): 251 (5), 221 (100), 207 (15), 177 (40), 133 (60), 104 (10). EA: C 12 H 30 O 4 Si 2 (294.54): calcd. C, 48.93; H, 10.27; found C, 48.99; H, 10.19. 3-(2,3-Bis(trimethylsiloxy)propoxy)propyldiethoxymethylsilane (Table 1, entry 9) was obtained as colourless oil (84%); 1 H NMR: (400 MHz, C 6 D 6 ): (ppm) = 0.10 (s, 12H), 0.20 (s, 9H), 0.59-0.82 (m, 2H), 1.13 (t, J = 7.0 Hz, 6H), 1.66-1.80 (m, 2H), 3.33 (t, J = 6.7 Hz, 2H), 3.38-3.57 (m, 2H), 3.66 (q, J = 7.0 Hz, 4H), 3.95-4.04 (m, 1H). 13 C NMR: (101 MHz, C 6 D 6 ): (ppm) = -5.0, -0.8, 0.2, 10.2, 18.3, 23.4, 57.7, 64.9, 72.8, 72.9, 73.7. MS (EI) m/z (rel. int.): 273 (3), 261 (5), 241 (100), 219 (20), 204 (20), 184 (20), 175 (60), 133 (90), 103 (20). EA: C 17 H 42 O 5 Si 3 (410.77): calcd. C, 49.71; H, 10.31; found C, 49.88; H, 10.29. 3-((2-Trimethylsiloxy)ethoxy)propyltriethoxysilane (Table 1, entry 10) was obtained as colourless oil (92%); 1 H NMR: (400 MHz, C 6 D 6 ): (ppm) = 0.12 (s, 9H), 0.75-0.83 (m, 2H), 1.16 (t, J = 7.0 Hz, 9H), 1.80-1.94 (m, 2H), 3.35 (t, J = 6.6 Hz, 2H), 3.42 (dd, J = 5.6, 4.9 Hz, 2H), 3.68 (dd, J = 5.6, 4.9 Hz, 2H), 3.79 (q, J = 7.0 Hz, 6H). 13 C NMR: (101 MHz, C 6 D 6 ): (ppm) = -0.6, 7.0, 18.2, 23.5, 58.1, 62.2, 72.2, 73.4. MS (EI) m/z (rel. int.): 250 (3), 205 (10), 175 (100), 163 (60), 131 (15), 119 (20), 73 (20). EA: C 14 H 34 O 5 Si 2 (338.59): calcd. C 49.66; H, 10.12; found C, 49.54; H, 10.09. 2-((4-Trimethylsiloxy)butoxy)ethyltriethoxysilane (Table 1, entry 11) was obtained as colourless oil (91%); 1 H NMR: (400 MHz, C 6 D 6 ): (ppm) = 0.08 (s, 9H), 1.15 (t, J = 7.0 Hz, 9H), 1.20-1.26 (m, 2H), 1.57-1.72 (m, 4H), 3.27-3.36 (m, 2H), 3.48-3.54 (m, 2H), 3.61-3.71 (m, 2H), 3.78 (q, J = 7.0 Hz, 6H). 13 C NMR: (101 MHz, C 6 D 6 ): (ppm) = -0.7, 13.3, 18.2, 26.5, 29.7, 58.1, 62.1, 66.5, 70.0. MS (EI) m/z (rel. int.): 279 (3), 237 (20), 207 (10), 193 (10), 163 (100),135 (15), 119 (20), 71 (40). EA: C 15 H 36 O 5 Si 2 (352.21): calcd. C, 51.09; H, 10.29; found C, 51.14; H, 10.36. S3
2-((2-Trimethylsiloxy)ethoxy)ethyltriethoxysilane (Table 1, entry 12) was obtained as colourless oil (93%); 1 H NMR: (400 MHz, C 6 D 6 ): (ppm) = 0.11 (s, 9H), 1.14 (t, J = 7.0 Hz, 9H), 1.19-1.29 (m, 2H), 3.42 (dd, J = 5.6, 4.8 Hz, 2H), 3.68 (t, J = 5.2 Hz, 2H), 3.69-3.73 (m, 2H), 3.76 (q, J = 7.0 Hz, 6H). 13 C NMR: (101 MHz, C 6 D 6 ): (ppm) = -0.6, 13.3, 18.2, 58.1, 62.2, 67.0, 71.8. MS (EI) m/z (rel. int.): 251 (15), 207 (25), 191 (15), 179 (10), 163 (100), 135 (10), 119 (15). EA: C 13 H 32 O 5 Si 2 (324.56): calcd. C, 48.11; H, 9.94; found C, 48.8; H, 9.89. 3-(2,2-Bis(trimethylsiloxymethyl)butoxy)propyltriethoxysilane (Table 1, entry 13) was obtained as colourless oil (87%); 1 H NMR: (400 MHz, C 6 D 6 ): (ppm) = 0.10 (s, 4H), 0.12 (s, 18H), 0.72-0.81 (m, 2H), 0.97 (t, J = 7.5 Hz, 3H), 1.17 (t, J = 7.0 Hz, 9H), 1.53-1.64 (m, 2H), 1.80-1.92 (m, 2H), 3.30-3.38 (m, 2H), 3.58 (s, 2H), 3.79 (q, J = 7.0 Hz, 6H). 13 C NMR: (101 MHz, C 6 D 6 ): (ppm) = -0.8, 6.9, 7.5, 18.2, 21.9, 23.4, 44.1, 58.1, 62.1, 70.0, 73.6. MS (EI) m/z (rel. int.): 280 (2), 249 (10), 237 (15), 205 (50), 191 (30), 163 (100), 119 (20), 73 (30). EA: C 21 H 50 O 6 Si 3 (482.87): calcd. C, 52.23; H, 10.44; found C, 52.28; H, 10.42. 3-(2,3-Bis(trimethylsiloxy)propoxy)propyltriethoxysilane (Table 1, entry 14) was obtained as colourless oil (85%); 1 H NMR: (400 MHz, C 6 D 6 ): (ppm) = 0.10 (s, 9H), 0.20 (s, 9H), 0.73-0.80 (m, 2H), 1.16 (t, J = 7.0 Hz, 9H), 1.66-1.97 (m, 2H), 3.35 (t, J = 7.1 Hz, 2H), 3.38-3.47 (m, 1H), 3.48-3.55 (m, 1H), 3.56-3.65 (m, 1H), 3.66-3.73 (m, 1H), 3.79 (q, J = 7.0 Hz, 6H), 3.91-4.07 (m, 1H). 13 C NMR: (101 MHz, C 6 D 6 ): (ppm) = -0.8, 0.2, 69, 18.2, 23.4, 58.1, 64.9, 72.8, 72.9, 73.5. MS (EI) m/z (rel. int.): 304 (5), 291 (5), 277 (15), 248 (5), 214 (40), 205 (70), 173 (50), 163 (100), 147 (50), 119 (30), 73 (50). EA: C 18 H 44 O 6 Si 3 (440.89): calcd. C, 49.05; H, 10.06; found C, 49.14; H, 10.01. S4
1 H and 13 C Spectra of Products: Spectra S5: 3-((2-Trimethylsiloxy)ethoxy)propylethoxydimethylsilane (Table 1, Entry 1) S5
Spectra S6: 2-((4-Trimethylsiloxy)butoxy)ethylethoxydimethylsilane (Table 1, entry 2) S6
Spectra S7: 2-((2-Trimethylsiloxy)ethoxy)ethylethoxydimethylsilane (Table 1, Entry 3) S7
Spectra S8: 3-(2,2-Bis(trimethylsiloxymethyl)butoxy)propylethoxydimethylsilane (Table 1, Entry 4) S8
Spectra S9: 3-(2,3-Bis(trimethylsiloxy)propoxy)propylethoxydimethylsilane (Table 1, Entry 5) S9
Spectra S10: 3-((2-Trimethylsiloxy)ethoxy)propyldiethoxymethylsilane (Table 1, Entry 6) S10
Spectra S11: 2-((4-Trimethylsiloxy)butoxy)ethyldiethoxymethylsilane (Table 1, Entry 7) S11
Spectra S12: 2-((2-Trimethylsiloxy)ethoxy)ethyldiethoxymethylsilane (Table 1, Entry 8) S12
Spectra S13: 3-(2,3-Bis(trimethylsiloxy)propoxy)propyldiethoxymethylsilane (Table 1, Entry 9) S13
Spectra S14: 3-((2-Trimethylsiloxy)ethoxy)propyltriethoxysilane (Table 1, Entry 10) S14
Spectra S15: 2-((4-Trimethylsiloxy)butoxy)ethyltriethoxysilane (Table 1, Entry 11) S15
Spectra S16: 2-((2-Trimethylsiloxy)ethoxy)ethyltriethoxysilane (Table 1, Entry 12) S16
Spectra S17: 3-(2,2-Bis(trimethylsiloxymethyl)butoxy)propyltriethoxysilane (Table 1, Entry 13) S17
Spectra S18: 3-(2,3-Bis(trimethylsiloxy)propoxy)propyltriethoxysilane (Table 1, Entry 14) S18