Hierarchical Micelles via Polyphilic Interactions: Hydrogen-Bonded Supramolecular Dendron and Double. Immiscible Polymers

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1 Supporting Information for: Hierarchical Micelles via Polyphilic Interactions: Hydrogen-Bonded Supramolecular Dendron and Double Immiscible Polymers Senbin Chen, a Bob-Dan Lechner, b Annette Meister b and Wolfgang H. Binder* a a : Chair of Macromolecular Chemistry, Faculty of Natural Science II (Chemistry, Physics and Mathematics), Martin Luther University Halle-Wittenberg, von-danckelmann-platz 4, Halle (Saale) D-06120, Germany; b : Physical Chemistry, Faculty of Natural Sciences II (Chemistry, Physics and Mathematics), Martin Luther University Halle-Wittenberg, von-danckelmann-platz 4, Halle (Saale) D-06120, Germany. Corresponding to W. H. Binder (wolfgang.binder@chemie.uni-halle.de). 1

2 Table of Contents Experimental section... 3 Materials... 3 Characterization methods... 3 Design, synthesis and structure characterization of Ba-(PnBuA-Ba) Solution polymerization of nbua to yield Ba-(nBuA-RAFT) Synthesis of compound Macromolecular transformation of Ba-(PnBuA-RAFT) 2 to Ba-(PnBuA-Ba) Design, polymerization and structure characterization of HW-P(nBuA-co-PFPA)-HW, HW-PPFPA-HW and HW-PnBuA-HW Solution copolymerization of nbua with PFPA to yield HW-P(nBuA-co-PFPA)-HW...12 Solution polymerization of PFPA to yield HW-PPFPA-HW...13 Solution polymerization of nbua to yield HW-PnBuA-HW...14 MALDI-TF MS measurements of HW-PnBuA-HW and HW-PPFPA-HW...15 Characterization of polymer self-assembly by 1 H NMR...18 Characterization of polymer self-assembly by DSY...21 Characterization of polymer self-assembly by AFM and TEM...21 References

3 Experimental section Materials All the chemicals were purchased from Alfa Aesar or Sigma-Aldrich. N-butyl acrylate (nbua) was filtered prior to passing through a column of basic aluminium oxide to remove inhibitors. 2,2,3,3,3-Pentafluoropropyl acrylate (PFPA) was purified by vacuum distillation. Unless otherwise indicated the other chemicals were used without further purification. Compound 1, 3 and HW-PI-HW were synthesized according to our previous report. [1] Characterization methods 1 H, 19 F NMR and DSY spectra were recorded on a Varian Unity Inova 500 (500 MHz) NMR spectrometer using CDCl 3 or toluene-d 8 as solvent. Polymers were analyzed by size exclusion chromatography (SEC) running in tetrahydrofuran (THF) at 35 C (flow rate: 1 ml. min -1 ), recorded on a GPCmax VE 2001 from Viscotek, equipped with a column set including a HHR-H Guard column, a CLM30111 column and a G2500HHR column. The average molar mass of polymers was derived from refractive index signals based on a polystyrene calibration curve. Matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TF MS) measurements were performed on Bruker Autoflex III system (Bruker Daltonics) operating in the linear mode. Data evaluation was carried out on DataAnalysis software. Ions were formed by laser desorption (smart beam laser at 355, 532, 808, and 1064 ± 5 nm; up to 50 Hz repetition rate), accelerated by a voltage of 20 kv and detected as positive ions. Samples 3

4 were prepared by mixing 50 μl of 2,5-dihydroxybenzoic acid at 20 g. L -1 in THF with 10 μl of polymer solution at 20 g. L -1 in THF. To enhance cationization of polymers, 1 μl of NaI at 10 g. L -1 in acetone was added to the solutions. Finally, 1 μl of the resulting mixture was spotted on a MALDI sample plate and air-dried. For imaging their topography by AFM, the substances were immobilized on a silicon solid support by spin coating films from a polymer solution in toluene (1 g/l). AFM imaging was carried out with a Multimode V atomic force microscope and a Nanoscope VII controller (Bruker Instruments, Santa Barbara, USA) operating in intermittent contact mode in air and at room temperature. TESPA-type silicon cantilevers (NanoWorld, Neuchâtel, Switzerland) with nominal spring constants of about 42 N/m and tip radii of smaller than 10 nm were used. The images were recorded with an acquisition speed of 6 µm/s (1 Hz line scan rate) and a resolution of 512 pixels 512 pixels. Prior to usage, the silicon substrates were freshly cleaned by piranha solution. Images were processed using Gwyddion software. Transmission electron microscopy (TEM) analyses were conducted with an EM 900 transmission electron microscope (Carl Zeiss Microscopy GmbH, berkochen, Germany). The samples were dissolved in toluene with concentration of 1 g/l and spread onto a Cu grid coated with a Carbon-film. After 1 min, excess solution was blotted off with filter paper, afterwards 5 μl of 1% aqueous uranyl acetate solution were deposited onto the grid and drained off after 1 min. TEM images were obtained from negatively stained samples. Micrographs were taken with a SSCCD SM-1k-120 camera (TRS, Moorenweis, Germany). 4

5 Design, synthesis and structure characterization of Ba-(PnBuA-Ba) 2. The synthesis of Ba-(PnBuA-Ba) 2 is realized as outlined in Figure S1. First, an esterification reaction is conducted between compound 1 and 2-bromopropionyl bromide using triethylamine as reagent and freshly distilled THF as solvent. The successful synthesis to yield compound 2 is confirmed by 1 H NMR spectroscopy indicating the new characteristic ester protons observed at 4.10 ppm (Figure S2). Meanwhile, Ba-(RAFT) 2 mediated solution polymerization of nbua in DMF at 65 o C to afford Ba-(PnBuA-RAFT) 2 is examined, consistent with controlled/living polymerization process, size exclusion chromatography (SEC) trace displays monodisperse peak as well as low polydispersity index (Ð, Figure S4, dash line). Then the targeted Ba-(PnBuA-Ba) 2 is readily accomplished between Ba-(PnBuA-RAFT) 2 and compound 2 relying on a one-pot two-step reaction, including aminolysis reaction of RAFT agent to yield reactive thiol groups, and subsequent in situ thiol-bromo click reaction at room temperature within one hour (Figure S1). 5

6 1 NEt 3, THF, rt, 16h, 67% yield 2 ne-pot two-step reaction Step1: Aminolysis Step2: Thio-bromo click reaction Ba-(PnBuA-RAFT) 2 Ba-(PnBuA-Ba) 2 Figure S1: Synthetic route to Ba-(PnBuA-Ba) 2. Solution polymerization of nbua to yield Ba-(nBuA-RAFT) 2. Solution polymerization of nbua was carried out using Ba-(RAFT) 2 as RAFT agent, and 2,2 -azobis(2-methylpropionitrile) (AIBN) as initiator. Typically, solution polymerization of nbua (0.28 ml, 2.0 x 10-3 mol) was carried out using AIBN (0.41 mg, 2.5 x 10-6 mol), Ba-(RAFT) 2 (22.1 mg, 2.5 x 10-5 mol), dimethylformamide (DMF, 0.28 ml) and trioxane (42 6

7 mg, 4.7 x 10-4 mol) as an internal reference for the measurement of monomer consumption via 1 H NMR. A stock solution was transferred into Schlenk tube which was thoroughly deoxygenated by 5 consecutive freeze-pump-thaw cycles. The tube was subsequently placed in an oil bath thermostated at 65 C. The reaction was stopped by plunging the tube into liquid nitrogen after 9 h. The polymer was subsequently precipitated twice into cold methanol/h 2 (2/1, v/v) in order to eliminate residual monomer and trioxane. The polymer was dried under vacuum and characterized by SEC (Figure S4) and 1 H NMR (Figure S3). The molar mass of pure Ba-(PnBuA-RAFT) 2 was evaluated using 1 H NMR (CDCl 3 ) from relative integration of the ester protons of the PnBuA backbone (--CH 2 -CH 2 -, 2nH, = 4.04 ppm, with n being the degree of polymerization) and the characteristic aromatic protons of Ba-(RAFT) 2 (2H, = 7.91 ppm). Synthesis of compound 2. The esterification reaction of compound 1 with 2-bromopropionyl bromide was performed in a round-bottomed flask under N 2 atmosphere. Typically, to a solution of compound 1 (1.3 g, 4 mmol) and triethylamine (0.48 g, 4.8 mmol) in anhydrous THF (80 ml), an excess of 2-brompropionyl bromide (1.0 g, 4.8 mmol) was added dropwise. The solution was stirred for 16h at room temperature. Dichloromethane was then added into the solution which was successively washed with saturated sodium bicarbonate, brine and water. The organic layer was dried over MgS 4 and the product was subsequently purified by silica column chromatography (eluent: CH 2 Cl 2 /MeH, 30/1, v/v) to give compound 2 as a white solid (1.23 g, 67%, Figure S2). 1 H NMR (CDCl 3 ) (ppm): 0.82(t, 6H), 1.16 (br, 16H), 1.64 (s, 4H),

8 (br, 2H), 1.74 (d, 3H), 1.96 (br, 4H), 4.08 (m, 2H), 4.32 (quart, 1H), 8.91 (s, 2H) , ppm Figure S2: 1 H NMR of compound 2 recorded in CDCl 3 at 27 o C. Macromolecular transformation of Ba-(PnBuA-RAFT) 2 to Ba-(PnBuA-Ba) 2 [2, 3] Ba-(PnBuA-Ba) 2 was prepared according to literature methods with modifications. Ba-(PnBuA-RAFT) 2 (M n NMR = 3.5 kda, M n SEC = 3.7 kda, Ð = 1.27, 80.0 mg, 2.0 x 10-5 mol), 2 (36.9 mg, 8.0 x 10-5 mol) and triethylamine (8.1 mg, 8.0 x 10-5 mol) were dissolved in 0.7 ml acetonitrile and purged with N 2 at room temperature for ~20 min. Hexylamine (6.1 mg, 6.0 x 10-5 mol), dissolved in 0.3 ml of acetonitrile, was added slowly into the above solution under N 2. After 1 hour, the solution was precipitated in cold methanol/h 2 (1/1, v/v) then purified by silica column chromatograph (acetonitrile/dichloromethane, 1/9, v/v), the obtained product Ba-(PnBuA-Ba) 2 was analyzed by 1 H NMR (Figure S3), SEC (Figure S4) and MALDI-TF MS (Figure S5). 8

9 Chemical Shift / ppm Figure S3: 1 H NMR spectra of Ba-(PnBuA-RAFT) 2 (bottom), and Ba-(PnBuA-Ba) 2 (top) at 27 C in CDCl 3 ([Ba-(PnBuA-RAFT) 2 ] = [Ba-(PnBuA-Ba) 2 ] = 2 mm). 9

10 RI Signal M n SEC = 4.5 kda, Ð = 1.22 M n SEC = 3.7 kda, Ð = Ve / ml Figure S4: SEC traces of Ba-(PnBuA-RAFT) 2 (dash line) and Ba-(PnBuA-Ba) 2 (solid line). The MALDI-TF MS spectrum of Ba-(PnBuA-Ba) 2 (Figure S5A), acquired in the linear mode, demonstrate the main series ( and ➌) separated by expected mass unit, revealing the repeating unit of the nbua monomer (Figure S5B). Besides main series, a minor distribution ( ) charged with different irons (Li + and K + ) is also observed. The series located at m/z average = Da, which corresponds to the assigned mid- and α,ω-ba functionalized PnBuA species [C 20 H 33 N 2 5 S-(C 7 H 12 2 ) m -C 32 H 54 N 2 7 -(C 7 H 12 2 ) n -C 20 H 33 N 2 5 S + Na] +, where m + n = 24, agree with the simulated pattern, m/z average = Da (Figure S5C). 10

11 Inset (A) (B) = Series, m + n = 24 Calculated mass: m/z = ➌ Mass (m/z) = = (C) ➌ measured simulated Mass (m/z) [Ba-(nBuA) m -Ba-(nBuA) n -Ba* + Na] + [Ba-(nBuA) m -Ba-(nBuA) n -Ba* - H + Li + K] + ➌ [Ba-(nBuA) m -Ba-(nBuA) n+1 -Ba* + Na] + *: α, ω-ends: Ba = C 20 H 33 N 2 5 S Mass (m/z) monomer: nbua = C 7 H 12 2 the middle: Ba = C 32 H 54 N 2 7 Figure S5: MALDI-TF MS of Ba-(PnBuA-Ba) 2 (A) full spectrum, (B) expansion and (C) simulation of the isotope pattern. Design, polymerization and structure characterization of HW-P(nBuA-co-PFPA)-HW, HW-PPFPA-HW and HW-PnBuA-HW n the other hand, for the design of the complementary (semi-fluorinated) building block, the controlled (co)polymerizations are realized via RAFT copolymerization starting from a chain transfer agent bearing HW moieties at both ends (compound 3, Figure S6), 11

12 AIBN DMF 65 o C N N co 22-m S S 24-n co m S F 2 C F 2 C CF CF 3 3 n N N HW-P(nBuA-co-PFPA)-HW N N S S S 3 N N AIBN DMF 65 o C N N S S S 66-x x N N F 2 C C F 3 AIBN DMF 65 o C N N S S S 40-y y F 2 C CF 3 CF 2 F 3 C HW-PnBuA-HW N N HW-PPFPA-HW Figure S6: Synthetic route to HW-P(nBuA-co-PFPA)-HW, HW-PPFPA-HW and HW-PnBuA-HW. Solution copolymerization of nbua with PFPA to yield HW-P(nBuA-co-PFPA)-HW Solution copolymerization of nbua with PFPA was carried out using compound 3 as RAFT agent and AIBN as initiator (Figure S6). Typically, solution copolymerization of nbua (0.054 ml, 3.8 x 10-4 mol) with PFPA (0.058 ml, 3.8 x 10-4 mol) was carried out using AIBN (0.25 mg, 1.5 x 10-6 mol), 3 (24.3 mg, 1.5 x 10-5 mol), dimethylformamide (DMF, 0.11 ml) and trioxane (42 mg, 4.7 x 10-4 mol) as an internal reference for the measurement of monomer consumption via 1 H NMR. A stock solution was transferred into a Schlenk tube, which was thoroughly deoxygenated by 5 consecutive freeze-pump-thaw cycles. The tube was subsequently placed in an oil bath thermostated at 65 C. The reaction was stopped by plunging the tube into liquid nitrogen after 5 h. The copolymer was subsequently precipitated twice into cold methanol/h 2 (2/1, v/v) in order to eliminate residual monomers and trioxane. The copolymer was dried under vacuum and characterized by 1 H NMR (Figure S11, middle), 12

13 29 Si NMR (Figure S7, bottom) and SEC (Figure S8, left). The molar mass of pure HW-P(nBuA-co-PFPA)-HW was evaluated using 1 H NMR (CDCl 3 ) from relative integration of the ester protons of the PnBuA backbone (--CH 2 -CH 2 -, 2mH, = 4.03 ppm, with m being the degree of polymerization), the PPFPA backbone (--CH 2 -CF 2 -, 2nH, = 4.52 ppm, with n being the degree of polymerization) and the characteristic aromatic protons of compound 3 (4H, = 7.64 ppm) Chemical shift / ppm Figure S7: 19 F NMR of HW-P(nBuA-co-PFPA)-HW (bottom) and HW-PPFPA-HW (top) at 27 C in CDCl 3. Solution polymerization of PFPA to yield HW-PPFPA-HW Solution polymerization of PFPA was carried out using compound 3 as RAFT agent and AIBN as initiator (Figure S6). Typically, solution polymerization of PFPA (0.16 ml, 3.8 x 10-4 mol) was carried out using AIBN (0.25 mg, 1.5 x 10-6 mol), 3 (24.3 mg, 1.5 x 10-5 mol), dimethylformamide (DMF, 0.11 ml) and trioxane (42 mg, 4.7 x 10-4 mol) as an internal reference for the measurement of monomer consumption via 1 H NMR. A stock solution was 13

14 transferred into a Schlenk tube, which was thoroughly deoxygenated by 5 consecutive freeze-pump-thaw cycles. The tube was subsequently placed in an oil bath thermostated at 65 C. The reaction was stopped by plunging the tube into liquid nitrogen after 5 h. The homopolymer was subsequently precipitated twice into cold methanol/h 2 (2/1, v/v) in order to eliminate residual monomers and trioxane. The homopolymer was dried under vacuum and characterized by 1 H NMR (Figure S12A), 29 Si NMR (Figure S7, top) and SEC (Figure S8, right). The molar mass of pure HW-PPFPA-HW was evaluated using 1 H NMR (CDCl 3 ) from relative integration of the ester protons of the PPFPA backbone (--CH 2 -CF 2 -, 2nH, = 4.52 ppm, with n being the degree of polymerization) and the characteristic aromatic protons of compound 3 (4H, = 7.64 ppm). Solution polymerization of nbua to yield HW-PnBuA-HW Solution polymerization of nbua was carried out using compound 3 as RAFT agent and AIBN as initiator (Figure S6). Typically, solution polymerization of nbua (0.11 ml, 7.6x 10-4 mol) was carried out using AIBN (0.25 mg, 1.5 x 10-6 mol), 3 (24.3 mg, 1.5 x 10-5 mol), dimethylformamide (DMF, 0.11 ml) and trioxane (42 mg, 4.7 x 10-4 mol) as an internal reference for the measurement of monomer consumption via 1 H NMR. A stock solution was transferred into a Schlenk tube, which was thoroughly deoxygenated by 5 consecutive freeze-pump-thaw cycles. The tube was subsequently placed in an oil bath thermostated at 65 C. The reaction was stopped by plunging the tube into liquid nitrogen after 5 h. The homopolymer was subsequently precipitated twice into cold methanol/h 2 (1/1, v/v) in order to eliminate residual monomers and trioxane. The homopolymer was dried under vacuum 14

15 UV Signal RI Signal and characterized by 1 H NMR (Figure S12B) and SEC (Figure S8). The molar mass of pure HW-PnBuA-HW was evaluated using 1 H NMR (CDCl 3 ) from relative integration of the ester protons of the PnBuA backbone (--CH 2 -CH 2 -, 2mH, = 4.03 ppm, with m being the degree of polymerization) and the characteristic aromatic protons of compound 3 (4H, = 7.64 ppm). HW-P(nBuA-co-PFPA)-HW HW-PnBuA-HW HW-PPFPA-HW Ve / ml Ve / ml Figure S8: SEC traces of (left): HW-P(nBuA-co-PFPA)-HW, HW-PPFPA-HW; and (right): HW-PnBuA-HW. MALDI-TF MS measurements of HW-PnBuA-HW and HW-PPFPA-HW Chain functionalization of PnBuA with HW moieties was then investigated via MALDI-TF MS spectrometry (Figure S9A), which was acquired in the linear mode. Figure S9B demonstrated the main series (2) and other minor distributions (1, 3 and 4) separated by expected mass unit, revealing the repeating unit of the nbua monomer. The trithiocarbonates elimination, well known due to the fragmentation of labile C-S bond during MALDI-TF mass analysis, resulted in a drastic decrease of the average molar mass (Mn SEC = 8.9 kda, Mn NMR = 10.0 kda). [1, 4] Nevertheless, the main isotopic pattern at m/z average = Da, which corresponded to the assigned HW moieties functionalized 15

16 Inset species [C 41 H 55 N 6 7 (C 7 H 12 2 ) 28 -S + Li] + agreed with the simulated pattern, m/z average = Da (Figure S9C). The observed isotopic patterns (m/z) of the three minor series (1, 3 and 4), as illustrated in Figure S9C, matched well with the simulated structures. (A) (B) N N x S S S y N N HW-PnBuA-HW 2 = = = Mass (m/z) 1 3 = = (C) , , measured 4392, , Mass (m/z) 4356, , , , [HW-(nBuA) 27 -CS 3 * - H + 2Na] + simulated 2 [HW-(nBuA) 28 -S* + Li] + 3 [HW-(nBuA) 28 -S* - H + Li + Na] + 4 [HW-(nBuA) 28 -S* - 2H + Li + 2Na] + *: α-ends: HW = C 41 H 55 N Mass (m/z) monomer: nbua = C 7 H 12 2 Figure S9: MALDI-TF MS of HW-PnBuA-HW (A) full spectrum, (B) expansion and (C) simulation of the isotope pattern. Based on the successful MALDI-TF MS measurement of HW-PnBuA-HW, we subsequently analyzed the semifluorinated homopolymer HW-PPFPA-HW (Figure S10A), again, a drastic decrease of the average molar mass (Mn SEC = 7.8 kda, Mn NMR = 9.6 kda) was observed, moreover, a significant suppression of high-mass chains was also found, which might due to the low impact velocity of the ions on the detector surface arising from 16

17 the low acceleration voltage, the high mass and/or fluorinated polymer nature. [5] Nevertheless, the mass spectrum illustrated the presence of main series (5), along with other minor series (1-4, and 6) as seen in Figure S10B. The mass difference between the m/z values of molecular ions in each main and minor series was equal to ~204.1 Da, revealing the repeating unit of the PFPA monomer. The observed isotopic patterns (m/z) of main series 5 located at m/z = Da, corresponding to the assigned species [C 41 H 55 N 6 7 (C 6 H 5 F 5 ) 17 -S 2H + Li + 2Na] + and the simulated pattern, m/z = 4295,5912 Da (Figure S10C). The observed isotopic patterns (m/z) of other minor series (1-4, and 6 Figure S10C), also matched well with the simulated structures. (A) (B) N N x F 2 C CF 3 S S S y CF 2 F 3 C N N HW-PPFPA-HW Inset 5 23 = = Mass (m/z) = (C) 4295, measured 4240, , , , Mass (m/z) simulated , , , , , [HW-(PFPA) 16 -CS 2 * - 3H + 3K + Li] + 2 [HW-(PFPA) 17 * - H + Na + Li] + 3 [HW-(PFPA) 17 -S* + Li ] + 4 [HW-(PFPA) 17 -S* - H + Li + Na] + 5 [HW-(PFPA) 17 -S* - 2H + Li + 2Na] + 6 [HW-(PFPA) 17 -S* - 3H + Li + 3Na] Mass (m/z) *: α-ends: HW = C 41 H 55 N 6 7 monomer: PFPA = C 6 H 5 F 5 2 Figure S10: MALDI-TF MS of HW-PPFPA-HW (A) full spectrum, (B) expansion and (C) simulation of the isotope pattern. 17

18 In the case of HW-P(nBuA-co-PFPA)-HW, it was an especially challenging polymer for both MALDI and ESI-TF mass spectrometry analysis and unfortunately we couldn t achieve the successful mass results. It is also known that mass techniques have several limitations for semifluorinated (co)polymer analysis, no standard sample preparation protocol or universal matrix has been developed so far. [5] Nevertheless, 1 H NMR analyses have clearly corroborated the presence of HW moieties in the polymer chains. Characterization of polymer self-assembly by 1 H NMR As seen in Figure S11, adding one equivalent of HW-P(nBuA-co-PFPA)-HW to a CDCl3 solution containing Ba-(PnBuA-Ba) 2 lead to significant downfield shift of the barbiturate protons (from 8.33 to ppm) as well as Hamilton wedge protons (from 8.55 and approximately 7.8 ppm to 9.80 and 9.42 ppm) which underline the association of multiple hydrogen bond arrays. Similarly, 1 H NMR spectra of the stoichiometric mixtures of Ba-(PnBuA-Ba) 2 with HW-PPFPA-HW, HW-PnBuA-HW or HW-PI-HW also reveal significant shifts for Ba and HW moieties protons demonstrating the formation of H-bonding complex (Figure S12). 18

19 Chemical shift / ppm Figure S11: 1 H NMR spectra of Ba-(PnBuA-RAFT) 2 (bottom), HW-P(nBuA-co-PFPA)-HW and a stoichiometric mixture of Ba-(PnBuA-RAFT) 2 with HW-P(nBuA-co-PFPA)-HW at 27 C in CDCl 3 ([Ba] = [HW] = 2 mm). The second imide peak of Hamilton wedge is overlapping with the aromatic protons in middle spectrum. 19

20 F E D C B A Chemical Shift / ppm Figure S12: 1 H NMR spectra of HW-PPFPA-HW (A), HW-PnBuA-HW (B), HW-PI-HW (C), a stoichiometric mixture of Ba-(PnBuA-Ba) 2 with HW-PPFPA-HW (D), a stoichiometric mixture of Ba-(PnBuA-Ba) 2 with HW-PnBuA-HW (E) and a stoichiometric mixture of Ba-(PnBuA-Ba) 2 with HW-PI-HW (E) at 27 C in CDCl 3 ([Ba] = [HW] = 2 mm). The second imide peak of Hamilton wedge is overlapping with the aromatic protons in A, B and C spectra. 20

21 D NMR (x m 2 /s) Characterization of polymer self-assembly by DSY Chemical shift (ppm) Figure S13: diffusion coefficient (D NMR ) distribution as a function of the chemical shift of the stoichiometric mixture of Ba-(PnBuA-Ba) 2 with HW-P(nBuA-co-PFPA)-HW in toluene-d 8 at 27 C, which reveal the D NMR distribution of nbuas unit in 1 H DSY spectrum (left) is nearly consistent with that of the PFPA units in 19 F DSY spectrum (right) Chemical shift (ppm) Table S1: Diffusion coefficient (D NMR ) and hydrodynamic radius (R h ) of supramolecular dendrons. D NMR R h ( m 2. s -1 ) (nm) Ba-(PnBuA-Ba) 2 + HW-P(nBuA-co-PFPA)-HW Ba-(PnBuA-Ba) 2 + HW-PnBuA-HW Ba-(PnBuA-Ba) 2 + HW-PPFPA-HW Ba-(PnBuA-Ba) 2 + HW-PI-HW Characterization of polymer self-assembly by AFM and TEM A B C 200 nm 200 nm 100 nm Figure S14: AFM height (A), phase (B) and TEM (C) imagines for the stoichiometric mixture of Ba-(PnBuA-RAFT) 2 with HW-P(nBuA-co-PFPA)-HW. 21

22 Height z / nm Height z / nm A B 40 C Lateral Distance / µm 400 nm 400 nm D E 30 F nm Lateral Distance / µm 400 nm Figure S15: AFM height (A,D), cross section (B,E) and phase (C,F) images of stoichiometric mixture of Ba-(PnBuA-Ba) 2 with HW-PPFPA-HW (top raw) or HW-PI-HW (bottom raw). 100 nm 100 nm 200 nm Figure S16: TEM imagines for the stoichiometric mixture of Ba-(PnBuA-Ba) 2 with HW-P(nBuA-co-PFPA)-HW. 100 nm Figure S17: TEM imagines for the stoichiometric mixture of Ba-(PnBuA-Ba) 2 with HW-PPFPA-HW. 22

23 100 nm 50 nm Figure S18: TEM imagines for the stoichiometric mixture of Ba-(PnBuA-Ba) 2 with HW-PI-HW. Figure S19: TEM imagines for the stoichiometric mixture of Ba-(PnBuA-Ba) 2 with HW-PnBuA-HW. References [1] S. Chen; Y. Deng; X. Chang; H. Barqawi; M. Schulz; W. H. Binder. Polym. Chem. 2014, 5, (8), [2] S. Chen; D. Ströhl; W. H. Binder. ACS Macro Lett. 2015, 4, [3] J. Xu; L. Tao; C. Boyer; A. B. Lowe; T. P. Davis. Macromolecules. 2010, 43, (1), [4] G. Hart-Smith; T. M. Lovestead; T. P. Davis; M. H. Stenzel; C. Barner-Kowollik. Biomacromolecules 2007, 8, (8), [5] L. Li. MALDI Mass Spectrometry for Syntetic Polymer Analysis 2010, John Wiley & Sons, Inc., Hoboken, New Jersey., ISBN: