supramolecular hyperbranched polymers for controllable self-assembly

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1 Electronic upplementary Material (EI) for Polymer Chemistry. This journal is The Royal ociety of Chemistry 2017 upplementary Information AB x -type amphiphilic macromonomer-based supramolecular hyperbranched polymers for controllable self-assembly Tingting Liu, huodong Wang, Yanli ong, Jiawei Li, Hongxia Yan, Wei Tian* The Key Laboratory of pace Applied Physics and Chemistry, Ministry of Education and haanxi Key Laboratory of Macromolecular cience and Technology, chool of cience, orthwestern Polytechnical University, Xi an, (P. R. China) *Correspondence to: W. Tian ( happytw_3000@nwpu.edu.cn), Tel. (fax): (+86) Table of Contents 1. ynthesis of MM 2. ynthesis of HP 3. elf-assembly of HP 4. Reversibility of HP self-assemblies 5. Reference 1

2 1 ynthesis and characterization of MM 1.1 ynthesis of oligo(gma-eda-β-cd) 5 - H (a) H i DCC,DMAP,CH 2 Cl 2,rt,1 6h (b) GMA-EDA-β -CD AIB,DMF,90 o C,48h i C 12 H 25 H H 5 (c) CH 3 CH,TBAF C 12 H 25 H H 5 i H H cheme 1 ynthetic routes of dodecyl-oligo(gma-eda-β-cd) ynthesis of -1-Dodecyl-'-(R,R'-dimethyl-R''-aceticacid) trithiocarbonate RAFT agent (DDEMETPA) DDEMETPA was synthesized according to the literature. [1] 1 H MR (CDCl 3,, ppm): 3.31 (2H, ( CH 2 CH 2 ); (6H, ( C C(CH 3 ) 2 ), (2H, CH 2 CH 2 ); (18H, CH 3 (CH 2 ) 9 ), 0.92 (3H, CH 3 (CH 2 ) 9 ). 13 C MR (CDCl 3,, ppm): ( C C(CH 3 ) 2 ); ( C C(CH 3 ) 2 ); (CH 3 (CH 2 ) 11 ); ( C C(CH 3 ) 2 ); (CH 3 (CH 2 ) 11 ); FTIR (KBr): cm -1 (m, CH 2 ); 1730 cm -1 (, C=); 1054 cm -1 (, C=). Electrospray ionization mass spectrometry (CDCl 3, m/z): calcd for C 17 H : ; found for [M+a] + :

3 Figure 1 1 H (a) and 13 C MR (b) spectra of DDEMETPA Figure 2 Electrospray ionization mass spectrum of DDEMETPA. The (M+a) + peak was found at m/z = , which is consistent with the calculated value m/z = Additionally, the (M+H) + peak was found at m/z = , and the (M+K) + peak was found at m/z = ynthesis of 3-(Trimethylsilyl)prop-2-1-Dodecyl- 2'-(R,R'-dimethyl- R''-ethyl ester)trithiocarbonate propanoate alkyne RAFT agent (DDEMETPA-TM) DDEMETPA-TM was prepared according to the literature. [4] 1 H MR (CDCl 3,, ppm): 4.73 (2H, ( CH 2 CH 2 ); 3.29 (2H, ( CH 2 CH 2 );1.78-3

4 1.70 (6H, ( C C(CH 3 ) 2 ); (18H, CH 3 (CH 2 ) 9 ), 0.9 (3H, CH 3 (CH 2 ) 9 ); 0.21 (9H, CH 2 C C i (CH 3 ) 3 ). 13 C MR (CDCl 3,, ppm): ( C C(CH 3 ) 2 ); ( CH 2 CH C i(ch 3 ) 3 ); ( CH 2 CH C i(ch 3 ) 3 ); ( CH 2 CH C i(ch 3 ) 3 ); ( C C(CH 3 ) 2 ); (CH 3 (CH 2 ) 11 ); (CH 3 (CH 2 ) 11 ); 1.02 ( CH 2 CH C i(ch 3 ) 3). FTIR (KBr): cm -1 (m, CH 2 ); 2186 cm -1 (, C C); 1742 cm -1 (, C=); 1250 cm -1 (, i ); 1054 cm -1 (, C=). Electrospray ionization mass spectrometry (CDCl 3, m/z): calcd for C 22 H i: 474.2; found for [M+a] + : Figure 3 1 H (a) and 13 C MR (b) spectra of DDEMETPA-TM. 4

5 Figure 4 Electrospray ionization mass spectrum of DDEMETPA-TM. The (M+a) + peak was found at m/z = which is consistent with the calculated value m/z = ynthesis of dodecyl-oligo(gma-eda-β-cd) 5 -TM Dodecyl-oligo(GMA-EDA-β-CD) 5 -TM was synthesized by RAFT. DDEMETPA-TM (47.4mg, 0.1 mmol), GMA-EDA-β-CD (1318 mg, 1 mmol), AIB (1.64 mg, 0.01 mmol) was dissolved in dried DMF (2 ml). The mixture was then stirred for 5 min and subjected to three freeze-vacuum-thaw cycles, and then the tube was immersed into an oil bath at 90 o C to perform polymerization. The mixture was dialyzed (molecular weight cut off: 3500) for 5 d. Dodecyl-oligo(GMA-EDA-β-CD) 5 -TM was obtained by lyophilization. Yields: 43%. 1 H MR (DM-d 6,, ppm): (50H, 2,3-H); (35H, 1-H); (35H, 6-H); (175H, 3,5,6-H and 2,4-H); 1.25 (6H, C(CH 3 ) 2 C ); 0.21 (9H, CH 2 C C i (CH 3 ) 3 ). 13 C MR (DM-d 6,, ppm): ( C(CH 3 ) C CH 2 and C(CH 3 ) 2 C CH 2 ); (C-1); (C-4); (C-2,3,5); (C-6); ( C(CH 3 ) C CH 2 ); ( C(CH 3 ) C CH 2, CH 3 (CH 2 ) 11 ); 1.02 ( CH 2 C C i(ch 3 ) 3 )). FTIR (KBr): 3300 cm -1 (, 5

6 H); 1640 cm -1 (, C=); 810 cm -1 (, C i). M n, EC/MALL =10400, M w, EC/MALL =13200, M w /M n = ynthesis of dodecyl-oligo(gma-eda-β-cd) 5 - ilyl deprotection was carried using a modified procedure reported by Haddleton et al. [5] Protected dodecyl-oligo(gma-eda-β-cd) 5 -TM (300 mg) was dissolved in DMF (10 ml) and the vial purged with nitrogen for 10 minutes. Acetic acid (10 mol%) was added and the solution was cooled to -20 o C. TBAF in THF (10 eq.) was added dropwise to the polymer solution and the reaction mixture was stirred at -20 o C for 30 minutes followed by stirring at room temperature for 16 hours. The mixture was dialyzed (molecular weight cut off: 3500) for 5 d. Dodecyl-oligo(GMA-EDA-β-CD) 5 - was obtained by lyophilization. Yields: 43%. 1 H MR (DM-d 6,, ppm): (50H, 2,3- H); (35H, 1-H); (35H, 6-H); (175H, 3,5,6-H and 2,4-H); 2.30 (1H, CH 2 C CH); 1.25 (6H, C(CH 3 ) 2 C ). 13 C MR (DM-d 6,, ppm): ( C(CH 3 ) C CH 2 and C(CH 3 ) 2 C CH 2 ); (C-1); (C-4); (C-2,3,5); (C-6); ( C(CH 3 ) C CH 2 ); ( C(CH 3 ) C CH 2, CH 3 (CH 2 ) 11 ). FTIR (KBr): 3300 cm -1 (, H); 1640 cm -1 (, C=). M n, EC/MALL =10200, M w, EC/MALL =13100, M w /M n =

7 Figure 5 FTIR spectra of DDMAT (a), DDEMETPA-TM (b), dodecyl-oligo(gma-edaβ-cd) 5 -TM (c), and dodecyl-oligo(gma-eda-β-cd) 5 - (d). Figure 6 1 H MR spectra of dodecyl-oligo(gma-eda-β-cd) 5 -TM (a) and dodecyloligo(gma-eda-β-cd) 5 - (b) 7

8 Figure 7 13 C MR spectra of dodecyl-oligo(gma-eda-β-cd) 5 -TM (a) and dodecyloligo(gma-eda-β-cd) 5 - (b) 1.2 ynthesis of tazo-pdma- 3 H Br Br Br DCC,DMAP,CH 2 Cl 2,rt,24h CuBr,PMEDTA,60 o C n 3 a3,dmf,ki,60 o C,24h n Br cheme 2 ynthetic routes of tazo-pdma

9 1.2.1 ythesis of 2-Bromo-2-methylpropionyl ester Azobenzene (BMPE- Azo) BMPE-Azo was synthesized by the esterification reaction of 4- phenylazophenol and 2-Bromo-2-methylpropionyl bromide. 4- phenylazophenol (1.03 g, 5.2 mmol), 4-dimethylaminopyridine (157 mg, 1.3 mmol), pyridine (449 mg, 5.7 mmol) was dissolved in dried CH 2 Cl 2 (20 ml). After cooling to 0 o C, 2-bromo-2-methylpropionyl bromide (715 mg, 5.7 mmol) was added dropwise to the solution. The mixture was then stirred at room temperature for 24 h. After completion of strring, deionized water (100 ml) was added in the mixture. The organic solution was washed with deionized water three times. After the organic solution was dried with anhydrous sodium sulfate, the CH 2 Cl 2 was removed by rotary evaporator. The crude product was purified by column chromatography (silica gel size: m,column diameter: 7 cm,column length: 30 cm) using petroleum acetone/diethyl ether (V/V=9/1) as elute, yielding orange solid. Yields: 75%. 1 H MR (CDCl 3,, ppm): (9H, proton in azobenzene); 2.11 (6H, C(CH 3 ) 2 Br). 13 C MR (CDCl 3,, ppm): ( C C(CH 3 ) 2 Br); (carbons in azobenzene); ( C CH(CH 3 ) 2 ); ( C C(CH 3 ) 2 Br). FTIR (KBr): 1640 cm -1 (, C=); 519 cm -1 (, C Br). Electrospray ionization mass spectrometry (CDCl 3, m/z): calcd for C 16 H Br: ; found for [M+a] + :

10 Figure 8 Electrospray ionization mass spectrum of BMPE-Azo. The (M+a) + peak was found at m/z = which is consistent with the calculated value m/z = Additionally, the (M+H) + peak was found at m/z = ynthesis of tazo-pdma 23 -Br A chlenk tube was added with DMA (1260 mg, 8 mmol), PMEDTA (70 mg, 0.4 mmol), CuBr (58 mg, 0.4 mmol), BMPE-Azo (121 mg, 0.4 mmol) and dry DMF (1 ml) under nitrogen. The mixture was then stirred for 5 min and subjected to three freeze-vacuum-thaw cycles, and then the tube was immersed into an oil bath at 60 o C to perform polymerization. After 2 h, the mixture was diluted with THF and passed though a neutral alumina column. The collected eluents were concentrated and precipitated into an excess of n- hexane. Yields: 65.1%. 1 H MR (CDCl 3,, ppm): (9H, protons in azobenzene); 4.09 (46H, C CH 2 CH 2 ); 2.59 (46H, C CH 2 CH 2 ); 2.30 (138H, CH 2 CH 2 (CH 3 ) 2 ); (46H, CH(CH 3 ) CH 2 ); 1.27 (6H, C(CH 3 ) 2 Br); (69H, CH(CH 3 ) CH 2 ). 13 C MR (CDCl 3,, ppm): ( C CH 2 CH 2, C C(CH 3 ) 2 ); (carbons in azobenzene); ( C 10

11 CH(CH 3 ) 2 ); ( C CH 2 CH 2, C CH 2 CH 2 ); ( CH 2 CH 2 (CH 3 ) 2 ); ( CH(CH 3 ) CH 2 ); ( C C(CH 3 ) 2 Br). FTIR (KBr): 1710 cm -1 (, C ); 519 cm -1 (, C Br). M n, EC/MALL =8800, M w, EC/MALL =9100, M w /M n = ynthesis of tazo-pdma 23-3 tazo-pdma 23-3 was obtained by the azidation of tazo-pdma 23 -Br. The typical procedure was as follows. tazo-pdma 23 -Br (240 mg, 0.02 mmol), a 3 (26 mg, 0.4mmol) was mixed with DMF (2 ml). The mixture was stirred at 50 o C for 48 h. After cooling to room temperature, the mixture was diluted with THF and passed though a neutral alumina column. The collected eluents were concentrated and precipitated into an excess of n-hexane. Yields: 80.1%. 1 H MR (CDCl 3,, ppm): (9H, proton in azobenzene); 4.05 (46H, C CH 2 CH 2 ); 2.56 (46H, C CH 2 CH 2 ); 2.28 (138H, CH 2 CH 2 (CH 3 ) 2 ); (46H, CH(CH 3 ) CH 2 ); 1.25 (6H, C(CH 3 ) 2 Br); (69H, CH(CH 3 ) CH 2 ). 13 C MR (CDCl 3,, ppm): ( C CH 2 CH 2, C C(CH 3 ) 2 ); (carbons in azobenzene); ( C CH(CH 3 ) 2 ); ( C CH 2 CH 2, C CH 2 CH 2 ); ( CH 2 CH 2 (CH 3 ) 2 ); ( CH(CH 3 ) CH 2 ); ( C C(CH 3 ) 2 Br). FTIR (KBr): 2204 cm -1 (, 3 ); 1710 cm - 1 (, C ). M n, EC/MALL =8500, M w, EC/MALL =9500, M w /M n =

12 Figure 9 FTIR spectra of BMPE-Azo (a), tazo-pdma 23 -Br (b), and tazo-pdma 23-3 (c) Figure 10 1 H MR spectra of BMPE-Azo (a), tazo-pdma 23 -Br (b), and tazo-pdma 23-3 (c) 12

13 Figure C MR spectra of BMPE-Azo (a), tazo-pdma 23 -Br (b), and tazo-pdma 23-3 (c) Figure 12 EC-MALL curve of tazo-pdma 23 -Br 13

14 1.3 ynthesis of MM C 12H 25 5 H H H In water C 12H 25 H H H H H H H H H 23 3 H H 23 3 H H H H cheme 3. ynthetic route of AB x -type macromonomer. Figure 13 UV absorption of tazo-pdma 23-3 upon stepwise addition of dodecyloligo(gma-eda-β-cd) 5 - (The concentration of dodecyl-oligo(gma-eda-β-cd) 5 - is M). 14

15 Figure 14 (a) Hydrodynamic diameter distribution of MM solutions (1.0 mg ml -1 ): initial state (black line); after 365 nm UV irradiation for 20 min (red line) and after 450 nm visible light irradiation for 20 min (blue line). (b) UV-vis spectra of MM solutions: before (green line) and after (blue line) UV light irradiation, after UV and visible light irradiation (black line). (c) Cycle change of absorption values at 330 nm of MM solutions by alternately imposing UV and visible light irradiation. 15

16 2 ynthesis of HP cheme 4 ynthetic route of HP. 16

17 3. elf-assembly of HP Figure 15 TEM images of HP-based unimolecular micelles (A-C) formed in 0.5 mol/l acl solutions and HP-based branched aggregates (D-F) formed in aqueous solutions. 17

18 Table 1 tructure parameters of HP self-assemblies in differnt solution conditions at 25 o C. ample olution conditions a D b av.,tem (nm) D h c (nm) DPI d M w e (10 6 g/mol) HP1-based unimolecular micelles 1 8.5± ± ± ± ±0.06 HP1-based unimolecular micelles ± ± ± ± ±0.04 HP1-based unimolecular micelles ± ± ± ± ±0.06 HP1-based unimolecular micelles ± ± ± ± ±0.07 HP1-based branched aggregates 2-210± ± ± ±0.03 HP2-based branched aggregates 2-235± ± ± ±0.06 HP3-based branched aggregates 2-345± ± ± ±0.01 HP4-based branched aggregates 2-387± ± ± ±0.04 a 1 and 2 repesent 0.5 mol/l acl solution and aqueous solution, respectively. b Average diameter determined by TEM. While D av.,tem values of HP selfassemblies in aqueous solutions can t be calculated by their TEM results due to the existence of branched morphology. c Hydrodynamic diameter determined by DL. d Diameter distribution determined by DL. e Apparent weight-average molecular weight (M w ) obtianed by Zimm plots determined by L. f econd virial coefficient (A 2 ) determined by L. g Average dn/dc values determined by refractive index detector. A 2,PU f (10-5 ) dn/dc g

19 Figure 16 TEM images of HP2-based self-assemblies in 0.1 mol/l acl solution (A), 1.0 mol/l acl solution (B), 0.5 mol/l a 2 4 solution (C) and 0.5 mol/l CsCl solution (D). The concentration of the sample is set as 1.0 mg ml -1. Figure 17 ize distributions and Zeta potentials of HP2-based self-assemblies under different salt conditions. 19

20 20

21 Figure 18 Zimm plots of MM and HP self-assemblies in 0.5 mol/l acl solutions and aqueous solutions at 25 o C. 4. Reversibility of HP self-assemblies Figure 19 TEM images of HP2-based unimolecular micelles in 0.5 mol/l acl solution (A-C) and HP2-based branched aggregates in deionized water (D-F) at 25 o C, respectively. (A, D) Without irradiation; (B, E) After 365 nm UV irradiation for 20 min; (C, F) ubsequent visible light irradiation for 20 min. 21

22 Figure 20 Confirmation of the reversibility of HP2-based branched aggregates in deionized water. (A) D z distribution of branched aggregates: before (black line) and after (red line) UV light irradiation, after UV and visible light irradiation (black line); (B) Cycle change of the D z values of branched aggregates by alternately imposing UV and visible light irradiation; (C) UV-vis spectra of branched aggregates: before (green line) and after (blue line) UV light irradiation, after UV and visible light irradiation (black line); (D) Cycle change of the absorbance values at λ=330 nm of branched aggregates by alternately imposing UV and visible light irradiation. 5 Reference [1] J. T. Lai, D. Filla, R. hea, Macromolecules 2002, 35,