How does A Tiny Terminal Alkynyl End Group Drive Fully Hydrophilic. Homopolymers to Self-Assemble into Multicompartment Vesicles and

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1 Electronic Supplementary Material (ESI) for Polymer Chemistry. This journal is The Royal Society of Chemistry 04 Electronic Supplementary Information for How does A Tiny Terminal Alkynyl End Group Drive Fully Hydrophilic Homopolymers to Self-Assemble into Multicompartment Vesicles and Flower-Like Complex Particles? Tingting Liu a, Wei Tian a *, Yunqing Zhu b, Yang Bai a, Hongxia Yan a, and Jianzhong Du b * a The Key Laboratory of Space Applied Physics and Chemistry, Ministry of Education and Shaanxi Key Laboratory of Macromolecular Science and Technology, School of Science, orthwestern Polytechnical University, Xi an, 00, P. R. of China b School of Materials Science and Engineering, Tongji University, 4800 Caoan Road, Shanghai, 0804, China Table of Contents. Synthesis of ATRP initiators. Synthesis of linear homopolymers 3. Synthesis of long chain hyperbranched homopolymer 4. Characterization of homopolymers 5. Self-assembly of homopolymers 6. References

2 . Synthesis of ATRP initiators Propargyl -bromoisobutyrate (I ), propargyl -bromo--methylpropionamide (I ), and benzyl - bromoisobutyrate (I 5 ) were synthesized according to the references, respectively. [S-S3] The characterization data were listed as following. For I : H MR (CDCl 3,, ppm): 4.8 (H, CH );.53 (H, CH C );.96 (6H, C C(CH 3 ) ). 3 C MR (CDCl 3,, ppm):. ( C C(CH 3 ) );.36 (CH C ); 5.36 (CH C ); 54.9 ( CH ); ( C C(CH 3 ) ); ( C C(CH 3 ) ). FTIR (KBr) 3404 cm - (, C H); 0 cm - (, C C); 34 cm - (, C ); 54 cm - (, C Br). For I : H MR (CDCl 3,, ppm):.5-6. (H, CH H ); 4.05 (H, CH H );. (H, CH C );.96 (6H, C C(CH 3 ) ). 3 C MR (CDCl 3,, ppm):.8 ( C C(CH 3 ) ); 6.3 (CH C );. (CH C ); 6.3 ( C C(CH 3 ) ); 3.60 ( C C(CH 3 ) ); 30.3 ( CH H ). FTIR (KBr) 340 cm - (, C H); 3 cm - (, C C); 535 cm - (, C Br). For I 5: H MR (CDCl 3,, ppm):.5-.5 (5H, Ph(H) ); 5. (H, Ph CH );.0-.4 (6H, C C(CH 3 ) ). 3 C MR (CDCl 3,, ppm):.48 ( C C(CH 3 ) ); 35.66, 8.60,.9 (Ph ); 65.3 (Ph CH ); 55.8 ( C C(CH 3 ) ); ( C C(CH 3 ) ). FTIR (KBr): cm - (, Ph(C H)); 9 cm - (, CH ); 34 cm - (, C ); cm - (, Ph(C=C)); 596 cm - (, C Br). Dipropargyl -bromo--methylpropionamide (I 3 ) was synthesized by the amidation reaction of Dipropargylamine and -Bromo--methylpropionyl bromide. Dipropargylamine (44 mg, 8 mmol), 4- dimethylaminopyridine (44 mg, mmol), pyridine (59 mg, 9.6 mmol) was dissolved in dried CH Cl (0 ml). After cooling to 0 o C, -bromo--methylpropionyl bromide (. g, 9.6 mmol) was added dropwise to the solution. The mixture was then stirred at room temperature for 4 h. After completion of strring, deionized water (00 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 Cl was removed by rotary evaporator. The crude product was purified by column chromatography (silica gel size: 0-00 m,column diameter: cm,column length: 30 cm) using petroleum ether/ethyl acetate (V/V=/) as elute, yielding dipropargyl--bromo--methylpropionyl bromo amide was yellow liquid. Yields: 66.4%. H MR (CDCl 3,, ppm): (4H, (CH C CH ) ); (H, (CH C CH ) ); (6H, C C(CH 3 ) ). 3 C MR (CDCl 3,, ppm):

3 69.36 ( C C(CH 3 ) );.8 ((CH C CH ) );.88 ((CH C CH ) ); 56.4 ( C C(CH 3 ) ); ((CH C CH ) ); 3.4 ( C C(CH 3 ) ). FTIR (KBr): 3 cm - (, C H); cm - (, C C); 59 cm - (, C Br). Electrospray ionization mass spectrometry (CDCl 3, m/z): calcd for C 0 H Br: 4.0; found for [M-H] + : 4.3. Elemental analysis (%): calcd for C 0 H Br: C 49.58, H 4.959, 5.85; found: C 45.56, H 4.56, Figure S Electrospray ionization mass spectrum of I 3. The (M-H) + peak was found at m/z = 4.3, which is consistent with the calculated value m/z =4.0.. Synthesis of linear homopolymers Synthesis of homopolymers -3. The typical procedure was as follows. A Schlenk tube was added with IPAM (.83 g, 5 mmol), Me 6 TER (5 mg, 0.5 mmol), CuBr ( mg, 0.5 mmol), I (03 mg, 0.5 mmol) and dry DMF (5 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 4 h, the mixture was diluted with THF and passed though a neutral alumina column. The solid was dissolved in distilled water and dialyzed (molecular weight cut off: 3500) for 5 d. Homopolymer was obtained by lyophilization. Yields: 45.%. H MR (DMS-d 6,, ppm): ( H CH(CH 3 ) ); 4.63 (H, HC C CH ); 3.86 ( H CH(CH 3 ) );.9 ( CH(C) CH );.45 ( CH(C) CH ); ( H CH (CH 3 ) ). 3 C MR (DMS-d 6,, ppm): 5.4 ( C H ); (HC C CH C ); ( H CH(CH 3 ) ); 3.06 ( CH(C) CH ); 3.69 ( H CH(CH 3 ) ). FTIR (KBr): 34 cm - (, C H); 330 cm - (, H); 4 cm - 3

4 (, C C); 0 cm - (, C ); 53 cm - (, C Br). Homopolymers including and 3 were synthesized with the similar procedure except for the ratio of IPAM to I. Their polymerization results were shown in Table S. Synthesis of homopolymers 4. The synthesis and purification procedures were similar with homopolymer except that I was used instead of I. Yields: 53.%. H MR (DMS-d 6,, ppm): ( H CH(CH 3 ) ); 5.56 (H, HC C CH ); 3.8 ( H CH(CH 3 ) );.8 (HC C CH );.9 ( CH(C) CH );.46 ( CH(C) CH );.05 ( H CH(CH 3 ) ). 3 C MR (DMS-d 6,, ppm): 4.8 ( C H CH(CH 3 ) ); (CH C CH H C ); 8.8 (CH C CH ); 3.49 (CH C CH ); 43.0 ( H CH(CH 3 ) ); 38.8 ( CH(C) CH ); 35. ( H C C(CH 3 ) ); 3.05 ( CH(C) CH ); 9.9 (CH C CH ); 3.63 ( C H CH(CH 3 ) ). FTIR (KBr): 35 cm - (, C H); 395 cm - (, H); 4 cm - (, C C); 0 cm - (, CH ); 5 cm - (, C Br). Synthesis of homopolymer 5. The synthesis and purification procedures were similar with homopolymer except that I 3 was used instead of I. Yields: 40.4%. H MR (DMS-d 6,, ppm):.5-.0 ( H CH(CH 3 ) ); 4.08 (4H, (CH C CH ) ); 3.94 (H, CH(C) CH Br); ( H CH(CH 3 ) );.6 (H, (CH C CH ) );.8-.5 ( CH(C) CH );.5-. ( CH(C) CH ); ( H CH(CH 3 ) ); 3 C MR (DMS-d 6,, ppm): 3.6 ( C H CH(CH 3 ) ); 4.55 ( H CH(CH 3 ) ); ( CH(C) CH ); ( CH(C) CH Br); 30.4 ( CH(C) CH );.55 ( H CH(CH 3 ) ); 0.94 (= C C(CH 3 ) ). FTIR (KBr): 3 cm - (, C H); 3308 cm - (, H); cm - (, C C); 646 cm - (, CH ); 50 cm - (, C Br). Synthesis of homopolymer. The synthesis and purification procedures were similar with homopolymer except that I 4 was used instead of I. Yields: 55.%. H MR (DMS-d 6,, ppm):.35 ( C H CH(CH 3 ) ); 4.03 (CH 3 CH ); 3.85 ( H CH(CH 3 ) );.99 ( CH(C) CH );.4 ( CH(C) CH );. ( C C(CH 3 ) );.06 ( H CH(CH 3 ) ). 3 C MR (DMS-d 6,, ppm): 3.86 ( C H CH(CH 3 ) ); (CH 3 CH C ); 4.0 ( H CH(CH 3 ) ); 36.9 ( CH(C) CH ); ( CH(C) CH ); 5. (CH 3 CH C ); 4.54 (CH 3 CH C );.4 ( H CH(CH 3 ) ). FTIR (KBr): 3490 cm - (, C H); 395 cm - (, H); 698 cm - (, 4

5 C ); 530 cm - (, C Br). Synthesis of homopolymer 8. The synthesis and purification procedures were similar with homopolymer except that I 5 was used instead of I. Yields: 49.%. H MR (DMS-d 6,, ppm):.36 (5H, Ph(H)); ( C H CH(CH 3 ) ); 5.03(Ph CH ); 3.84 ( H CH(CH 3 ) );.98 ( CH(C) CH );.43 ( CH(C) CH );.05 ( H CH(CH 3 ) ). 3 C MR (DMS-d 6,, ppm): 3.88 ( C H CH(CH 3 ) ); 64.3 (Ph CH C ); (Ph(C)); (Ph CH C ); 4.8 ( H CH(CH 3 ) ); ( CH(C) CH );.80 ( H CH(CH 3 ) ). FTIR (KBr): 933 cm - (, CH ); 09 cm - (, C ); 49 cm - (, Ph(C=C)); 53 cm - (, C Br). Synthesis of homopolymer 9. A mixture of I (03 mg, 0.5 mmol), EGMA 45 (.85 g, 6 mmol) and PMDETA (86 mg, 0.5 mmol) in 5 ml H /methanol (:, v/v) was bubbled with nitrogen gas for 5 min at 0 o C, CuBr (4 mg, 0. mmol) and CuCl (54 mg, 0.4 mmol) was then added. The solution was bubbled with nitrogen gas for 30 min at 0 o C and sealed under atmosphere. The polymerization was conducted at 0 o C for 4 h. It was terminated by exposing to air and diluting with THF. After passing through a neutral alumina column and evaporating most of solvent, the residues were precitated and dried in a vacuum 3 d. Homopolymer 9 was obtained. Yields: 45.%. H MR (DMS-d 6,, ppm): 4. (H, HC C CH ); 4.0 ( C CH CH ); 3.59 ( C CH CH ); 3.5 ( CH CH ); 3.44 (6H, C C(CH 3 ) ); 3.3 ( CH 3 );.5 ( CH C(CH 3 ) ); ( CH C(CH 3 ) ). 3 C MR (DMS-d 6,, ppm):.6 ( C CH CH );.56 ( C CH CH );.8 ( CH CH ); 69.5 ( C CH CH ); ( CH C(CH 3 ) ); 59.4 ( CH 3 ); 45.3 ( CH C(CH 3 ) );.56 ( C C(CH 3 ) ). FTIR (KBr): 398 cm - (, C H); 80 cm - (, C ); 30 cm - (, C ); 54 cm - (, C Br). Synthesis of homopolymer 0. The synthesis and purification procedures were similar with homopolymer 9 except that I was used instead of I. Yields: 5.%. H MR (DMS-d 6,, ppm): 4.4 (H, HC C CH ); 4.0 ( C CH CH ); 3.6 ( C CH CH ); 3.5 ( CH CH ); 3.44 ( C C(CH 3 ) ); 3.3( CH 3 );.5 ( CH C(CH 3 ) ); ( CH C(CH 3 ) ). 3 C MR (DMS-d 6,, ppm):.86 ( C CH CH );.58 ( C CH CH );.9 ( CH CH ); ( C CH CH ); ( CH C(CH 3 ) ); 5

6 59.35 ( CH 3 ); 46.0 ( CH C(CH 3 ) ). FTIR (KBr): 33 cm - (, C H); 865 cm - (, C ); 8 cm - (, HC ); 530 cm - (, C Br). Synthesis of homopolymer. The synthesis and purification procedures were similar with homopolymer 9 except that I 3 was used instead of I. Yields: 69.%. H MR ( DMS-d 6,, ppm): 5.5 ( CH C(CH 3 ) Br); 4. ((HC C) CH H ); 4.0 ( C CH CH ); 3.4 ( C CH CH ); 3.5 ( CH CH ); 3.4 ( C C(CH 3 ) ); 3.4 ( CH 3 );.3 ((HC C CH ) H );.5-.4 ( CH C(CH 3 ) );.-0.6 ( CH C(CH 3 ) ). 3 C MR (DMSd 6,, ppm):.09 ( C CH CH );.4 ( C CH CH ); 69.8 ( CH CH ); 6.84 ( C CH CH ); 63.9 ( CH C(CH 3 ) ); 58. ( CH 3 ); 44. ( CH C(CH 3 ) ); 6.40 ( C C(CH 3 ) ). FTIR (KBr): 39 cm - (, C H); 8 cm - (, C ); 8 cm - (, HC ); 5 cm - (, C Br). 3. Synthesis of long chain hyperbranched homopolymer Synthesis of 5. To obtain 6, 5 was first synthesized by the azidation of 5. The typical procedure was as follows. 5 (50 mg, 0.03 mmol), a 3 (4 mg, 0.3 mmol) was mixed with DMF ( ml). The mixture was stirred at 50 o C for 48 h. After cooling to room temperature, the mixture was dialyzed (molecular weight cut off: 3500) for 3 d. Homopolymer 5 was obtained by lyophilization. H MR (DMS-d 6,, ppm):.5-.0 ( H CH(CH 3 ) ); 4.08 (4H, (CH C CH ) ); ( H CH(CH 3 ) ); 3.85 (H, CH(C) CH 3 );. (H, (CH C CH ) );.8-.5 ( CH CH );.4 ((CH C CH ) );.5-. ( CH(C) CH ); ( H CH(CH 3 ) ). 3 C MR ( DMS-d 6,, ppm) 3.0 ( C H ); 4.50 ( H CH(CH 3 ) ); 36.0 ( CH(C) CH );.4 ( H CH(CH 3 ) ). FTIR (KBr): 3 cm - (, C H); 3308 cm - (, H); cm - (, C C); 646 cm - (, C H ). Synthesis of LCHBH 6. 5 (88 mg, 0.09 mmol), CuBr (6.6 mg, mmol), PMDETA (.6 mg, mmol), and DMF (.5 ml) was added into a Schlenk tube. 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 00 o C. After 4h, the mixture was diluted with THF and passed though a neutral alumina column. The solid was dissolved in distilled water and dialyzed (molecular weight cut off: 8000~4000) for 5 days. 6

7 Homopolymer 6 was obtained by lyophilization. Yields: 65.5%. H MR (DMS-d 6,, ppm):.96 (methine proton in,,3-triazole ring);. ( H CH(CH 3 ) ); 5.35 ( CH, protons in,,3- triazole ring); 3.84 ( H CH(CH 3 ) );.4 ((CH C CH ) );.98 ( CH(C) CH );.46 ( CH(C) CH );.05 ( H CH(CH 3 ) ). 3 C MR (DMS-d 6,, ppm): 3.4 ( C H CH(CH 3 ) ); 3.,.06 (C=C, carbons in the,,3-triazole ring); 4.65 ( H CH(CH 3 ) ); ( CH(C) CH ); 3.50 ( CH, carbon attached to,,3-the triazole ring); 8.98 ( CH(C) CH );.48 ( H CH(CH 3 ) ). FTIR (KBr): 3308 cm - (, H); 3 cm - (, C H); cm - (, C C); 646 cm - (, HC ). 4. Characterization of homopolymers Table S. Molecular structure parameters of homopolymers Code Sample M a w M a n M w /M a n DP b n HP/HPI c (kda) (kda) (wt%) PIB-PIPAM-Br PIB-PIPAM-Br PIB-PIPAM-Br PMPA-PIPAM-Br DiPMPA-PIPAM-Br DiPMPA m -HBPIPAM EIB-PIPAM-Br BIB-PIPAM-Br PIB-PEGMA 45 -Br PMPA-PEGMA 45 -Br DiPMPA-PEGMA 45 -Br a Molecular weight and molecular weight distributions determined by SEC/MALLS, d Degree of polymerization determined by M n, c The weight fraction of the hydrophobic end group in the whole hydrophilic homopolymer.

8 Figure S SEC/MALLS curves of homopolymers. (A) homopolymers -4 (in DMF); (B) homopolymers 5, 5 and 6 (in DMF); (C) homopolymers and 8 (in DMF); (D) homopolymers 9- (in THF). 8

9 8 H 43 8 Br 4.0 n- 5 H 6 8. H DMS.8 (A) n H H 6 8 n H (B) 6, n H n 3 5 H (C) (ppm) Figure S3 H MR spectra of homopolymers 5 (A), 5 (B) and 6 (C) in DMS-d6. 5. Self-assembly of homopolymers Figure S4 TEM and AFM images of homopolymers 4 and 5 (A-B for TEM and E-F for AFM) aqueous solutions with a concentration of 0. mg/ml at 0 oc; (C-D) Typical magnification images of A-B. 9

10 0

11 Figure S5 Relationship between the fluorescence intensity ratio (I 3 /I ) and homopolymer concentration in aqueous solution (Inset: fluorescence emission spectrum of pyrene). A-K represent homopolymers -.

12 D z (nm) Figure S6 Typical intensity-averaged diameter distributions of the homopolymers and 8 (A and B) aqueous solutions with a concentration of 0. mg/ml at 0 o C Figure S Variation in the transmittance at 550 nm of the homopolymer aqueous solution (A: -3; B: 4-6) with a concentration of 0. mg/ml as a function of temperature.

13 Figure S8. FTIR-ATR spectra of homopolymers, 3-6 (A-E) solution in THF and their self-assemblies in H with a concentration of 0. mg/ml at 0 o C 3

14 Scheme S Chemical structure of doxorubicin hydrochloride 6. References [S] Tsarevsky,. V.; Sumerlin, B. S.; Matyjaszewski, K. Macromolecules 005, 38, [S] Song, J.; Lee, E.; Cho, B. K. J. Polym. Sci.: Part A: Polym. Chem. 03, 5, [S3] Hovestad,. J.; Koten, G. V.; Bon, S. A. F.; Haddleton, D. M. Macromolecules 000, 33,