This journal is The Royal Society of Chemistry 212 Supplementary Information Host Guest Chemistry of Linked -Cyclodextrin Trimers and Adamantyl Substituted Poly(acrylate)s in Aqueous Solution Hanh-Trang Nguyen, a Duc-Truc Pham, a Stephen F. Lincoln,* a Jie Wang, b Xuhong Guo, b Christopher J. Easton c and Robert K. Prud homme d a School of Chemistry and Physics, University of Adelaide, Adelaide, SA 55, Australia Email: stephen.lincoln@adelaide.edu.au b State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 2237, China c Research School of Chemistry, Australian National University, Canberra, ACT 2, Australia d Department of Chemical Engineering, Princeton University, Princeton, NJ 8544 (USA) 1
This journal is The Royal Society of Chemistry 212 Mass spectra 1 358.151 8 Relative intensity 6 4 3558.173 3596.132 2 352 354 356 358 36 362 m/z Fig. S1. Mass spectrum of β-cd 3 bz, positive ion mode, singly charged species 3558.173 [M+H] +, 358.151 [M+Na] + and 3596.132 [M+K] +. 1 8 1777.564 Relative intensity 6 4 2 176 177 178 179 18 181 m/z Fig. S2. Mass spectrum of β-cd 3 bz, negative ion mode, doubly charged species 1777.564 [M-2H] 2-. 1 378.148 8 Relative intensity 6 4 3724.117 2 3686.159 368 369 37 371 372 373 m/z Fig. S3. Mass spectrum of β-cden 3 bz, positive ion mode, singly charged species 3686.159 [M+H] +, 378.148 [M+Na] + and 3724.117 [M+K] +. 2
This journal is The Royal Society of Chemistry 212 1 8 3684.259 Relative intensity 6 4 2 368 369 37 371 m/z Fig. S4. Mass spectrum of β-cden 3 bz, negative ion mode, singly charged specie 3684.259 [M-H] -. 1 H and 13 C NMR Spectra Fig. S5. 1 H NMR spectrum of 1,3,5 trinitrophenyl benzene in d 6 -dimethylsufoxide. Fig. S6. 1 H NMR spectrum of β-cd 3 bz in D 2 O. Fig. S7. 13 C NMR spectrum of β-cd 3 bz in D 2 O. 3
This journal is The Royal Society of Chemistry 212 Fig. S8. 1 H NMR spectrum of β-cden 3 bz in D 2 O. Fig. S9. 13 C NMR spectrum of β-cden 3 bz in D 2 O. 2D NOESY 1 H NMR Spectra Ar H -CD H1 HOD -CD H2-6 AD H2-4 -CD H2-6 PAA, AD H Fig. S1. 2D NOESY 1 H NMR (6 MHz) spectrum (mixing time 3ms) of a solution 1. x 1-3 mol dm -3 in β-cd 3 bz and 1. wt. % in 3% substituted PAAAD such that the adamantyl substituent concentration is 3. x 1-3 mol dm -3 in D 2 O (pd 7. phosphate buffer, I =.1 mol dm -3 ) at 298.2K. The rectangle encloses the crosspeaks arising from interaction between the annular β-cd H3,5,6 protons of β-cd 3 bz and the adamantyl substituent H1-4 protons of PAAAD. 4
PAA, AD H en N-CH2 Ar H AD H2-4 HOD -CD H1 Electronic Supplementary Material (ESI) for Polymer Chemistry This journal is The Royal Society of Chemistry 212 PAA, AD H hn -CH2 -CD H1 Ar H hn N-CH2 AD H2-4 HOD Fig. S11. 2D NOESY 1H NMR (6 MHz) spectrum (mixing time 3ms) of a solution 1. x 1-3 mol dm-3 in β-cd3bz and 1. wt. % in 3% substituted PAAADen such that the adamantyl substituent concentration is 3. x 1-3 mol dm-3 in D2O (pd 7. phosphate buffer, I =.1 mol dm-3) at 298.2K. The rectangle encloses the crosspeaks arising from interaction between the annular β-cd H3,5,6 protons of β-cd3bz and the adamantyl substituent H1-4 protons of PAAADen. A B Fig. S12. 2D NOESY 1H NMR (6 MHz) spectrum (mixing time 3ms) of a solution 1. x 1-3 mol dm-3 in β-cd3bz and 1. wt. % in 3% substituted PAAADhn such that the adamantyl substituent concentration is 3. x 1-3 mol dm-3 in D2O (pd 7. phosphate buffer, I =.1 mol dm-3) at 298.2K. Rectangles A and B enclose the cross-peaks arising from interaction between the annular β-cd H3,5,6 protons of βcd3bz and the adamantyl substituent H1-4 protons and the tether hexyl 2-5 methylene protons of PAAADhn, respectively. 5
-CD H1 PAA, AD H A ddn -CH2 Ar H ddn N-CH2 AD H2-4 HOD Electronic Supplementary Material (ESI) for Polymer Chemistry This journal is The Royal Society of Chemistry 212 B PAA, AD H -CD H1HOD Ar H en N-CH2 AD H2-4 Fig. S13. 2D NOESY 1H NMR (6 MHz) spectrum (mixing time 3ms) of a solution 1. x 1-3 mol dm-3 in β-cd3bz and 1. wt. % in 3% substituted PAAADddn such that the adamantyl substituent concentration is 3. x 1-3 mol dm-3 in D2O (pd 7. phosphate buffer, I =.1 mol dm-3) at 298.2K. Rectangles A and B enclose the cross-peaks arising from interaction between the annular β-cd H3,5,6 protons of βcd3bz and the adamantyl substituent H1-4 protons and the tether dodecyl 2-11 methylene protons of PAAADddn, respectively. Fig. S14. 2D NOESY 1H NMR (6 MHz) spectrum (mixing time 3ms) of a solution 1. x 1-3 mol dm-3 in β-cden3bz and 1. wt. % in 3% substituted PAAAD such that the adamantyl substituent concentration is 3. x 1-3 mol dm-3 in D2O (pd 7. phosphate buffer, I =.1 mol dm-3) at 298.2K. The rectangle encloses the crosspeaks arising from interaction between the annular β-cd H3,5,6 protons of βcden3bz and the adamantyl substituent H1-4 protons of PAAAD. 6
-CD H1 en N-CH2 AD H2-4 HOD Ar H PAA, AD H Electronic Supplementary Material (ESI) for Polymer Chemistry This journal is The Royal Society of Chemistry 212 -CD H1 A ddn -CH2 PAA, AD H AD H2-4 Ar H HOD ddn N-CH2 Fig. S15. 2D NOESY 1H NMR (6 MHz) spectrum (mixing time 3ms) of a solution 1. x 1-3 mol dm-3 in β-cden3bz and 1. wt. % in 3% substituted PAAADen such that the adamantyl substituent concentration is 3. x 1-3 mol dm-3 in D2O (pd 7. phosphate buffer, I =.1 mol dm-3) at 298.2K. The rectangle encloses the crosspeaks arising from interaction between the annular β-cd H3,5,6 protons of βcden3bz and the adamantyl substituent H1-4 protons of PAAADen. B Fig. S16. 2D NOESY 1H NMR (6 MHz) spectrum (mixing time 3ms) of a solution 1. x 1-3 mol dm-3 in β-cden3bz and 1. wt. % in 3% substituted PAAADddn such that the adamantyl substituent concentration is 3. x 1-3 mol dm-3 in D2O (pd 7. phosphate buffer, I =.1 mol dm-3) at 298.2K. Rectangles A and B enclose the cross-peaks arising from interaction between the annular β-cd H3,5,6 protons of β-cden3bz and the adamantyl substituent H1-4 protons and the tether dodecyl 2-11 methylene protons of PAAADddn, respectively. 7
This journal is The Royal Society of Chemistry 212 ITC Data -1 1 2 3 4 5 6 7 8 9 1-5 µj/s -1-1 kj/mol -CD -2-3 -4..5 1. 1.5 2. 2.5 3. 3.5 4. 4.5 5. 5.5 [ -CD]/[adamantyl substituent] Fig. S17. Isothermal titration calorimetry (ITC) data for.13 wt. % PAAAD ([adamantyl substituent] = 4. 1-4 mol dm -3 ) with β-cd (1.6 1-2 mol dm -3 ) in aqueous phosphate buffer at ph 7. (I =.1 mol dm -3 ) at 298.2 K. The top section shows the raw ITC experimental plot. The bottom section shows a solid curve representing the best fit to the data points of an algorithm for an equilibrium analogous to that shown in eqn. 1 in the published text for the complexation by β-cd of the adamantyl substituent guests of PAAAD. 8
This journal is The Royal Society of Chemistry 212-1 1 2 3 4 5 6 7 8 9 1 11-1 -2 µj/s -3-4 -5-6 -5 kj/mol -CD -1-15 -2..5 1. 1.5 2. [ -CD]/[adamantyl substituent] Fig. S18. Isothermal titration calorimetry (ITC) data for.37 wt. % PAAADhn ([adamantyl substituent] = 1.1 1-3 mol dm -3 ) with β-cd (8.22 1-3 mol dm -3 ) in aqueous phosphate buffer at ph 7. (I =.1 mol dm -3 ) at 298.2 K. The top section shows the raw ITC experimental plot. The bottom section shows a solid curve representing the best fit of an algorithm. The bottom section shows a solid curve representing the best fit to the data points of an algorithm for an equilibrium analogous to that shown in eqn. 1 in the published text for the complexation by β-cd of the adamantyl substituent guests of PAAADhn. 9
This journal is The Royal Society of Chemistry 212-1 1 2 3 4 5 6 7 8 9 1-1 µj/s -2-3 -4 kj/mol -CD -5-1 -15..5 1. 1.5 2. 2.5 3. 3.5 4. [ -CD]/[adamantyl substituent] Fig. S19. Isothermal titration calorimetry (ITC) data for.21 wt. % PAAADddn ([adamantyl substituent] = 6. 1-4 mol dm -3 ) with β-cd (1.6 1-2 mol dm -3 ) in aqueous phosphate buffer at ph 7. (I =.1 mol dm -3 ) at 298.2 K. The top section shows the raw ITC experimental plot. The bottom section shows a solid curve representing the best fit to the data points of an algorithm for an equilibrium analogous to that shown in eqn. 1 in the published text for the complexation by β-cd of the adamantyl substituent guests of PAAADddn. 1
This journal is The Royal Society of Chemistry 212-1 1 2 3 4 5 6 7 8 9 1-5 µj/s -1-5 kj/mol -CD 3 bz -1-15 -2-25..25.5.75 1. 1.25 [ -CD 3 bz]/[adamantyl substituent] Fig. S2. Isothermal titration calorimetry (ITC) data for.13 wt. % PAAAD ([adamantyl substituent] = 4. 1-4 mol dm -3 ) with β-cd 3 bz (2.1 1-3 mol dm -3 ) in aqueous phosphate buffer at ph 7. (I =.1 mol dm -3 ) at 298.2 K. The top section shows the raw ITC experimental plot. The bottom section shows a solid curve representing the best fit to the data points of an algorithm for an equilibrium analogous to that shown in eqn. 2 in the published text for the complexation by β- CD 3 bz of the adamantyl substituent guests of PAAAD.. 11
This journal is The Royal Society of Chemistry 212-1 1 2 3 4 5 6 7 8 9 1-1 µj/s -2-3 -4-1 kj/mol -CD 3 bz -2-3 -4-5 -6-7 -8..25.5.75 [ -CD 3 bz]/[adamantyl substituent] Fig. S21. Isothermal titration calorimetry (ITC) data for.2 wt. % PAAADen ([adamantyl substituent] = 6. 1-4 mol dm -3 ) with β-cd 3 bz (2.1 1-3 mol dm -3 ) in aqueous phosphate buffer at ph 7. (I =.1 mol dm -3 ) at 298.2 K. The top section shows the raw ITC experimental plot. The bottom section shows a solid curve representing the best fit to the data points of an algorithm for an equilibrium analogous to that shown in eqn. 2 in the published text for the complexation by β- CD 3 bz of the adamantyl substituent guests of PAAADen. 12
This journal is The Royal Society of Chemistry 212-1 1 2 3 4 5 6 7 8 9 1-1 µj/s -2-3 -4-1 kj/mol -CD 3 bz -2-3 -4-5 -6-7..25.5.75 [ -CD 3 bz]/[adamantyl substituent] Fig. S22. Isothermal titration calorimetry (ITC) data for.21 wt. % PAAADddn ([adamantyl substituent] = 6. 1-4 mol dm -3 ) with β-cd 3 bz (2.1 1-3 mol dm -3 ) in aqueous phosphate buffer at ph 7. (I =.1 mol dm -3 ) at 298.2 K. The top section shows the raw ITC experimental plot. The bottom section shows a solid curve representing the best fit to the data points of an algorithm for an equilibrium analogous to that shown in eqn. 2 in the published text for the complexation by β- CD 3 bz of the adamantyl substituent guests of PAAADddn. 13
This journal is The Royal Society of Chemistry 212-1 1 2 3 4 5 6 7 8 9 1 (a) (b) µj/s -1-2 -5-1 kj/mol -CDen 3 bz -15-2 -25-3 -35..25.5.75 1. 1.25 [ -CDen 3 bz]/[adamantyl substituent] Fig. S23. Isothermal titration calorimetry (ITC) data for.13 wt. % PAAAD ([adamantyl substituent] = 4. 1-4 mol dm -3 ) with β-cden 3 bz (2.17 1-3 mol dm -3 ) in aqueous phosphate buffer at ph 7. (I =.1 mol dm -3 ) at 298.2 K. The top section shows the raw ITC experimental plot where (a) is the data for dilution of β- CDen 3 bz and (b) is that for the titration obtained as described in the published text. The bottom section shows a solid curve representing the best fit to the corrected titration data points of an algorithm for an equilibrium analogous to that shown in eqn. 3 in the published text for the complexation by β-cden 3 bz of the adamantyl substituent guests of PAAADddn. 14
This journal is The Royal Society of Chemistry 212-1 1 2 3 4 5 6 7 8 9 1 1 (a) (b) -1-2 µj/s -3-4 kj/mol -CDen 3 bz -5-6 -1-2 -3-4 -5-6 -7-8 -9..25.5.75 [ -CDen 3 bz]/[adamantyl substituent] Fig. S24. Isothermal titration calorimetry (ITC) data for.2 wt.% PAAADen ([adamantyl substituent] = 6. 1-4 mol dm -3 ) with β-cden 3 bz (2.17 1-3 mol dm -3 ) in aqueous phosphate buffer at ph 7. (I =.1 mol dm -3 ) at 298.2 K. The top section shows the raw ITC experimental plot where (a) is the data for dilution of β- CDen 3 bz and (b) is that for the titration obtained as described in the published text. The bottom section shows a solid curve representing the best fit to the corrected titration data points of an algorithm for an equilibrium analogous to that shown in eqn. 3 in the published text for the complexation by β-cden 3 bz of the adamantyl substituent guests of PAAADen. 15
This journal is The Royal Society of Chemistry 212-1 1 2 3 4 5 6 7 8 9 1 1 (a) (b) -1 µj/sec -2-3 kj/mole -CDen 3 bz -4-5 -6-1 -2-3 -4-5 -6-7 -8-9..25.5.75 [ -CDen 3 bz]/[adamantyl substituent] Fig. S25. Isothermal titration calorimetry (ITC) data for.2 wt. % PAAADhn ([adamantyl substituent] = 6. 1-4 mol dm -3 ) with β-cden 3 bz (2.17 1-3 mol dm -3 ) in aqueous phosphate buffer at ph 7. (I =.1 mol dm -3 ) at 298.2 K. The top section shows the raw ITC experimental plot where (a) is the data for dilution of β- CDen 3 bz and (b) is that for the titration obtained as described in the published text. The bottom section shows a solid curve representing the best fit to the corrected titration data points of an algorithm for an equilibrium analogous to that shown in eqn. 3 in the published text for the complexation by β-cden 3 bz of the adamantyl substituent guests of PAAADhn. 16
This journal is The Royal Society of Chemistry 212-1 1 2 3 4 5 6 7 8 9 1 1 (a) (b) -1 µj/s -2-3 -4-5 -1 kj/mol -CDen 3 bz -2-3 -4-5 -6-7..25.5.75 [ -CDen 3 bz]/[adamantyl substituent] Fig. S26. Isothermal titration calorimetry (ITC) data for.21 wt. % PAAADddn ([adamantyl substituent] = 6. 1-4 mol dm -3 ) with β-cden 3 bz (2.17 1-3 mol dm -3 ) in aqueous phosphate buffer at ph 7. (I =.1 mol dm -3 ) at 298.2 K. The top section shows the raw ITC experimental plot where (a) is the data for dilution of β- CDen 3 bz and (b) is that for the titration obtained as described in the published text. The bottom section shows a solid curve representing the best fit to the corrected titration data points of an algorithm for an equilibrium analogous to that shown in eqn. 3 in the published text for the complexation by β-cden 3 bz of the adamantyl substituent guests of PAAADddn. 17
This journal is The Royal Society of Chemistry 212 Table S1. Variation of the chemical shift of the aromatic 1 H resonance of -CDen 3 bz with concentration. a,b [ -CDen 3 bz] mol dm -3 ppm b 1.2 1-2 8.44 9.46 1-3 8.46 7.44 1-3 8.47 5.84 1-3 8.47 4.59 1-3 8.48 3.61 1-3 8.48 2.83 1-3 8.49 2.23 1-3 8.49 a In D 2 O phosphate buffer at pd 7., I =.1 mol dm -3 and 298.2 K. b Chemical shift downfield of HOD resonance at 4.79 ppm which is downfield of the methyl resonance of sodium-3(trimethylsilyl)propanesulfonate at. ppm (H. E. Gottlieb, V. Kotlyar and A Nudelman, J. Org. Chem., 1997, 62, 7512-7515) Determined at 3 MHz. 18