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Facile Synthesis of Stable, Water Soluble, Dendron-Coated Gold Nanoparticles

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Facile Synthesis of Stable, Water Soluble, Dendron-Coated Gold Nanoparticles Electronic Supplementary Material (ESI) for Nanoscale. This journal is © The Royal Society of Chemistry 2017 Facile Synthesis of stable, water soluble, dendron-coated gold nanoparticles Alan E. Enciso, Giovanni Doni, Riccardo Nifosi, Ferruccio Palazzesi, Roberto Gonzalez, Ashley A. Ellsworth, Jeffrey L. Coffer, Amy V. Walker, Giovanni M. Pavan, Ahmed Mohamed, & Eric E. Simanek Table of Contents General Experimental 3 G0-Aniline Dendron 4 SI Figure 1. 1H NMR 5 SI Figure 2. 13C NMR 6 SI Figure 3. Mass Spectra 7 G1-Aniline Dendron 8 SI Figure 4. 1H NMR 9 SI Figure 5. 13C NMR 10 SI Figure 6. Mass Spectra 11 G2-Aniline Dendron 12 SI Figure 7. 1H NMR 13 SI Figure 8. 13C NMR 14 SI Figure 9. Mass Spectra 15 G0-Diazonium Dendron 16 1 SI Figure 10. H NMR (CD3CN) 17 1 SI Figure 11. H NMR ((CD3CN+CD3OD) 18 SI Figure 12. 13C NMR 19 G1-Diazonium Dendron 20 1 SI Figure 13. H NMR (CD3CN) 21 1 SI Figure 14. H NMR (CD3CN+CD3OD) 22 SI Figure 15. 13C NMR 23 G2-Diazonium Dendron 24 1 SI Figure 16. H NMR( CD3CN) 25 1 SI Figure 17. H NMR (CD3CN+CD3OD) 26 SI Figure 18. 13C NMR 27 G0@AuNP and BOC-G0@AuNP 28 SI Figure 19. Deprotected G0@AuNP 1H NMR 29 SI Figure 20. Deprotected G0@AuNP 13C NMR 30 SI Figure 21. BOC- G0@AuNP 1H NMR 31 SI Figure 22. BOC- G0@AuNP 13C NMR 32 G1@AuNP 33 SI Figure 23. BOC- G1@AuNP 1H NMR 34 SI Figure 24. BOC- G1@AuNP 13C NMR 35 1 SI Figure 25. G1@AuNP 1H NMR 36 SI Figure 26. G1@AuNP 13C NMR 37 G2@AuNP 38 SI Figure 27. BOC- G2@AuNP 1H NMR 39 SI Figure 28. BOC- G2@AuNP 13C NMR 40 SI Figure 29. G2@AuNP 1H NMR 41 SI Figure 30. G2@AuNP 13C NMR 42 SI Figure 31. Infrared of diazonium salt moieties. 43 SI Figure 32. UV of G0@AuNP 44 SI Figure 33. TEM images of G0@AuNP 45 SI Figure 34. UV of G1@AuNP 46 SI Figure 35. TEM images of G1@AuNP 47 SI Figure 36. UV of G2@AuNP 48 SI Figure 37. TEM images of G2@AuNP 49 Stability Studies 50 SI Figure 38. Stability of G0@AuNP at different conditions 51 SI Figure 39. Stability of G0@AuNP at different conditions 52 SI Figure 40. Stability of G0@AuNP at different conditions 53 SI Figure 41. TEM images of surface coating 54 SI Figure 42. TGA of G0@AuNP 55 SI Figure 43. TGA of G2@AuNP 56 Computational Details and Associated Figures 57 SI Figure 44. Model for dendron packing 58 SI Figure 45. Dendron spacing as a function of time 59 Table 1. Main features of the simulated NP-dendron systems 60 SI Figure 46. RMDS as a function of simulation time 62 General Experimental for XPS and TOF SIMS 64 SI Figure 47. Photoelectron spectra of G0@Au 65 SI Figure 48. Photoelectron spectra of G1@Au 66 SI Figure 49. Photoelectron spectra of G2@Au 67 SI Figure 50. Mass spectra of G0@Au 68 SI Figure 51. Mass spectra of G1@Au 69 SI Figure 52. Mass spectra of G2@Au 70 Contributions: AM conceived the experiments and supervised elements of execution. AEB executed the synthetic chemistry under the direction of EES (TCU). GD, RN, FP developed the computational strategies for the system under the direction of GMP (SUPSI). RG collected TEM images under the direction of JLC (TCU). AAE collected XPS and SIMS data under the direction of AVW (UT Dallas), who should be contacted for questions concerning these efforts. 2 General Experimental Three different generation triazine dendrons (G0, G1, G2) were synthesized by known methodsa. Each one of the dendrons was reacted overnight with a THF solution of 4-(aminomethyl)aniline. Afterwards the purification was accomplished by column chromatography. The dendrons containing aniline were reacted with H[AuCl4]•3H2O and [NO]PF6 in acetonitrile in order to generate the diazonium moieties; the product was recovered by precipitation with diethyl ether. The corresponding diazonium salt was reduced with a solution 0.1M of NaBH4 to form the grafted gold nanoparticles that were recovered by either filtration or centrifugation. All the species where analyzed under UV-vis, NMR, TEM besides of verifying the formation of the diazonium salts by IR. a Enciso, A. E.; Abid, Z. M.; Simanek, E. E. Polym. Chem., 2014, 5, 4635. 3 G0-aniline dendron G0-Triazine Dendron (0.400 g, 0.532 mmol) was added to a solution of 4-(aminomethyl)aniline (0.325 g, 2.6 mmol) in THF (4 mL). Afterwards the solution was heated while stirring for 16 hours at 75ºC in a capped vessel. The crude product was purified by column chromatography. The solvent system used was the following: 100% DCM to 95:5 DCM: MeOH to give G0- 1 aniline (0.347 g, 83%) as a yellowish oil. H NMR (400 MHz, CDCl3) δ 7.04-7.03 (dd, J = 7.6 Hz, 2H, m-aniline), 6.58-6.56 (dd, J = 8.3 Hz, 2H, o-aniline), 4.38 (br, 2H, aniline-CH2-NH- triazine) 3.73-3.39 (m, 28H, CH2OCH2CH2OCH2CH2OCH2, C3N3-NHCH2CH2CH2O), 3.17 (br 13 m, 4H, BocNHCH2), 1.77-1.68 (m, 8H, OCH2CH2CH2), 1.44 (s, 18H, C(CH3)3); C NMR (100 MHz, CDCl3) δ 165.9 (C3N3), 156.1 (CO), 145.6 (H2N-C(aniline)), 129.1 (p-aniline), 128.7 (m- aniline), 115.0 (o-aniline), 78.7 (C(CH3)3), 70.5 (OCH2CH2O), 70.2 (OCH2CH2O), 70.1 (OCH2CH2O), 69.4 (CH2CH2CH2O), 69.2 (CH2CH2CH2O), 44.1 (aniline-CH2-NH-triazine), 38.4 (CH2CH2CH2O), 38.1 (CH2CH2CH2O) 29.6 (NHCH2CH2CH2O), 29.5 (NHCH2CH2CH2O), 28.4 (C(CH3)3); MS (ESI-TOF) calcd for C40H71N9O10 837.53, found 838.54. 4 SI Figure 1 - 1H NMR of G0 - Aniline Dendron 5 SI Figure 2- 13C NMR of G0 - Aniline Dendron 6 SI Figure 3 - Mass Spectra of G0- Aniline Dendron 7 G1-aniline G1-Triazine Dendron (0.400 g, 0.202 mmol) was added to a solution of 4-(aminomethyl)aniline (0.123 g, 1 mmol) in THF (2 mL). Afterwards the solution was heated while stirring for 16 hours at 75ºC in a capped vessel. The crude product was purified by column chromatography. The solvent system used was the following: 100% DCM to 90:10 DCM: MeOH to give G1-aniline 1 (0.347 g, 83%) as a yellowish oil. H NMR (400 MHz, CDCl3) δ 7.07-7.05 (dd, J = 7.7 Hz, 2H, m-aniline), 6.60-6.58 (dd, J = 8.3 Hz, 2H, o-aniline), 4.40 (br, 2H, aniline-CH2-NH-triazine) 3.63-3.39 (m, 88H, CH2OCH2CH2OCH2CH2OCH2, C3N3-NHCH2CH2CH2O), 3.20 (br m, 8H, 13 BocNHCH2), 1.78-1.71 (m, 24H, OCH2CH2CH2), 1.45 (s, 36H, C(CH3)3); C NMR (100 MHz, CDCl3) δ 166.0 (C3N3), 156.0 (CO), 145.6 (H2N-C(aniline)), 129.1 (p-aniline), 128.7 (m- aniline), 115.0 (o-aniline), 78.8 (C(CH3)3), 70.5 (OCH2CH2O), 70.2 (OCH2CH2O), 70.1 (OCH2CH2O), 69.5 (CH2CH2CH2O), 69.2 (CH2CH2CH2O), 44.1 (aniline-CH2-NH-triazine), 38.5 (CH2CH2CH2O), 38.0 (CH2CH2CH2O), 29.6 (two lines, NHCH2CH2CH2O), 28.4 (C(CH3)3); MS (ESI-TOF) calcd for C96H177N23O26, 2068.32; found 2070.33. 8 SI Figure 4 - 1H NMR of G1- Aniline Dendron 9 SI Figure 5 - 13C NMR of G1- Aniline Dendron 10 SI Figure 6 - Mass Spectra of G1- Aniline Dendron 11 G2-aniline G2-Triazine Dendron (0.400 g, 0.089 mmol) was added to a solution of 4-(aminomethyl)aniline (0.055 g, 0.450 mmol) in THF (2 mL). Afterwards the solution was heated while stirring for 16 hours at 75ºC in a capped vessel. The crude product was purified by column chromatography. The solvent system used was the following: 100% DCM to 90:10 DCM: MeOH to give G2- 1 aniline (0.327 g, 80%) as a yellowish oil. H NMR (400 MHz, CDCl3) δ 7.02-7.00 (dd, J = 7.6 Hz, 2H, m-aniline), 6.56-6.54 (dd, J = 8.3 Hz, 2H, o-aniline), 4.36 (br, 2H, aniline-CH2-NH- triazine) 3.69-3.36 (m, 208H, CH2OCH2CH2OCH2CH2OCH2, C3N3-NHCH2CH2CH2O), 3.16 13 (br m, 16H, BocNHCH2), 1.76-1.68 (m, 56H, OCH2CH2CH2), 1.38 (s, 72H, C(CH3)3); C NMR (100 MHz, CDCl3) δ 165.8 (C3N3), 156.0 (CO), 145.7 (H2N-C(aniline)), 129.1 (not found, p- aniline), 128.7 (m-aniline), 115.0 (o-aniline), 78.7 (C(CH3)3), 70.5 (OCH2CH2O), 70.2 (OCH2CH2O), 70.1 (two lines, OCH2CH2O), 69.4 (CH2CH2CH2O), 69.2 (two lines, CH2CH2CH2O), 44.1 (aniline-CH2-NH-triazine), 38.4 (CH2CH2CH2O), 38.0 (two lines, CH2CH2CH2O), 29.6 (two lines, NHCH2CH2CH2O), 28.4 (C(CH3)3); MS (ESI-TOF) calcd for C208H389N51O58, 4529.90; found 4531.96. 12 SI Figure 7 - 1H NMR of G2 Aniline Dendron 13 SI Figure 8 - 13C NMR of G2 Aniline Dendron 14 SI Figure 9 - Mass Spectra of G2 Aniline Dendron 15 G0-Diazonium H[AuCl4]•3H2O (0.094 g, 0.240 mmol) and [NO]PF6 (0.042 g, 0.240 mmol) were added to a solution of G0-aniline (0.200 g, 0.240 mmol) in CD3CN (2.4 mL) while stirring. The reaction was kept at 0ºC for 4 hours and was left to reach room temperature in a 2 hours period time.
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