Supporting Information

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1 S1 Supporting Information Assembly of Amphiphilic Hyperbranched Polymeric Ionic Liquids in Aqueous Media at Different ph and Ionic Strength Volodymyr F. Korolovych, a Petr A. Ledin, a Alexandr Stryutsky, b Valery V. Shevchenko, b Oleh Sobko, b Weinan Xu, a Leonid A. Bulavin, c Vladimir V. Tsukruk* a a School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332, USA. b Institute of Macromolecular Chemistry of the National Academy of Sciences of Ukraine, Kharkivske Shosse 48, Kyiv 02160, Ukraine. c Taras Shevchenko National University of Kyiv, Volodymyrska Str. 64, Kyiv, Ukraine. * Corresponding Author vladimir@mse.gatech.edu, Phone: , Fax:

2 S2 SI1. Synthesis of HBP-ILs. a) Hyperbranched aliphatic carboxylic acids (C 18 H 37 ) 16 -НВР-(СООH) g ( g-equiv) of n-octadecylisocyanate was added to 3.46 g ( g-equiv) of HBP in 14 ml of DMF at 80 C and reaction was held at stirring for 12 h till complete consumption of isocyanate groups (according to FT-IR spectroscopy) (see Scheme 1). Further g ( g-equiv) of phthalic anhydride was added to the resultant solution followed by reaction during 20 h at 80 C being stirred as we described earlier [36]. The solvent was partially evaporated under reduced pressure and the remaining product was re-precepitated from acetone to hexane and dried at C. Yield 6.02 g (60.2%). The content of carboxyl groups was determined by acid-base titration. COOH group content: 6.5% (calculated 6.7%). The product is a clear light brown solid, readily soluble in acetone, benzene, ethyl acetate, tetrahydrofuran (THF), chloroform, DMF, and is insoluble in acetonitrile, hexane, and water. b) Amphiphilic hyperbranched carboxylate protic HBP-ILs. CIm 16 was obtained via neutralization of 1.79 g ( g-equiv) of acid (C 18 H 37 ) 16 -НВР- (СООH) 16 with 0.21 g ( g-equiv) N-methylimidazole in 6 ml of acetone at intensive stirring for 5 min at ambient temperature. The solvent was partially evaporated and the product was precipitated in acetonitrile. The obtained HBP-IL was dried at C. Yield 1.47 g (73.3%). The product is a clear, light brown viscous liquid, readily soluble in acetone, ethyl acetate, benzene, chloroform, DMF, DMSO, THF, and insoluble in acetonitrile. FT-IR: ν C-O-C, ν С-О bonds of carboxylic groups ( cm -1 ), δ sy CH 3 (1375 cm -1 ), δ CH 2, as CH 3 (1468 cm -1 ), ν ar C-C ( cm -1 ), ν C=O (1732 cm -1 ), the overtones of N-H bonds of heterocycles ( cm -1 ), ν N-H + ( cm -1 ), ν al С-Н ( cm -1 ), ν ar С-Н (3070 cm -1 ), ν С-Н bonds of imidazolium cation (3145 cm -1 ) [44]. 1 H NMR (DMSO-d 6 ): (CH 3 -CH 2 -), 1.04 (CH 3 -C), (-CH 2 -), (-CCH 2 OCH 2 CH 2 OC(O)-), 3.66 (-N(CH 3 )-), (-CH 2 OC(O)-), 6.98 (- NH + -CH=CH-N(CH 3 )-), 7.18 (-NH + -CH=CH-N(CH 3 )-), (-Ar-H, -NH + =CH-

3 S3 N(CH 3 )-), 8.07 (-NH + -CH=NH-). GPC: M w =4684 g/mol, Mn=2756 g/mol, M w /M n = 1.7. The CIm 16 is abbreviations for this type of HBP-IL. CTr 16 was synthesized in the same manner using 1,2,4-1H-triazole as a base. Yield 1.60 g (79.8%). The obtained compound is a clear light brown viscous liquid, readily soluble in acetone, ethyl acetate, chloroform, DMF, DMSO, THF, and acetonitrile and insoluble in water. FT-IR: ν C-O-C, ν С-О bonds of carboxylic groups ( см -1 ), δ sy CH 3 (1371 см -1 ), δ CH 2 (1468 cm -1 ), ν ar C-C ( cm -1 ), ν C=O (1731 cm -1 ), the overtones of N-H bonds of heterocycles ( cm -1 ), ν N-H + ( cm -1 ), ν al С-Н ( cm -1 ), ν ar С-Н (3072 cm -1 ), ν С-Н bonds of imidazolium cation (3136 cm -1 ) [36]. 1 H NMR (DMSO-d 6 ): (CH 3 -CH 2 -), 1.04 (CH 3 -C), (- CH 2 -), ((-CH 2 -,-CCH 2 OCH 2 CH 2 OC(O)-), (-CH 2 OC(O)-), (-Ar-H, -NH=CH-NH-). GPC: M w =5429 g/mol, Mn=4845 g/mol, M w /M n = The CTr 16 is abbreviations for this type of HBP-IL. c) Hyperbranched amphiphilic polymeric sulfonic acid (C 18 H 37 ) 16 -НВР-(SО 3 H) g ( g-equiv) of n-octadecylisocyanate was added to g ( g- equiv) of HBP in 8 ml of DMF at 80 C and reaction was held at stirring for 12 h till complete consumption of isocyanate groups (according to FT-IR spectroscopy). Following g ( g-equiv) of 2-sulfobenzoic acid cyclic anhydride was added to the resultant solution and reaction was held at stirring during 20 h at 80 C. The solvent was partially removed under reduced pressure (1-3 mm Hg) and the synthesized product was reprecipitated from acetone to acetonitrile and further dried at С. Yield g (48.8%). The content of sulfonic groups was determined by acid-base titration [36]. SO 3 H content: 10.8% (calculated 11.4%). The product is a clear light brown solid, readily soluble in water, THF, DMF, DMSO and insoluble in acetonitrile, hexane. d) Amphiphilic hyperbranched sulfonate protic HBP-ILs. SIm 16 was synthesized via neutralization of g ( g-equiv) of acid (C 18 H 37 ) 16 - НВР-(SО 3 H) 16 with g ( g-equiv) of N-methylimidazole in 5 ml of THF at intensive stirring for 3-5 min at ambient temperature. The solvent was partially

4 S4 evaporated and the product was precipitated in acetonitrile. The resultant PIL was dried at o C. Yield g (88.8%). The product is a pale yellow solid with temperature of transition to fluid state equal to C, well soluble in acetone, chloroform, benzene, THF, DMF, DMSO, and insoluble in ether and acetonitrile. FT-IR: ν S=O (1019 cm -1 ), ν C-O-C, ν С-О bonds of carboxylate groups ( cm -1 ), δ sy CH 3 (1379 cm -1 ), δ CH 2, as CH 3 (1469 cm -1 ), ν ar C-C ( cm -1 ), ν C=O (1734 cm -1 ), ν al С-Н ( cm -1 ), ν ar С-Н (3072 cm -1 ), ν С-Н bonds of imidazolium cation (3152 cm - 1 ) [36]. 1 H NMR (DMSO-d 6 ): (CH 3 -), 1.43 (CH 3 -C), (-CH 2 -), ((-CH 2 -,-CCH 2 OCH 2 CH 2 OC(O)-), 3.73 (-N(CH 3 )-), (-CH 2 OC(O)-), 7.06 (-NH + - CH=CH-N(CH 3 )-), 7.19 (-NH + -CH=CH-N(CH 3 )-), , (-Ar-H, -NH + =CH- N(CH 3 )-), 8.35 (-NH + -CH=NH-). 13 C NMR (CDCl 3 ): (CH 3 -CH 2 -), (CH 3 -C-), (CH 3 -CH 2 -CH 2 -), 26.86, 29.40, 29.75, 31.95, (-CH 2 -CH 2 -CH 2 -), (-N- CH 3 ), (-C(O)-NH-CH 2 -CH 2 -), 46.67, (C(CH 3 )(CH 2 -)), (-C-CH 2 - O-), , , , (-C=C-C=), (-NH-CH=N-), (-C=O). The SIm 16 is abbreviations for this type of HBP-IL. STr 16 was synthesized in the same manner using 1,2,4-1H-triazole as a base. The obtained compound is a dark brown solid with temperature of transition to fluid state equal to C, readily soluble in chloroform, benzene, DMF, DMSO, THF, and insoluble in ethanol and acetonitrile. Yield g (89.5%). FT-IR: ν S=O (1019 cm -1 ), ν C-O-C, ν С-О bonds of carboxylate groups ( cm -1 ), δ sy CH 3 (1374 cm -1 ), δ CH 2, as CH 3 (1469 cm -1 ), ν ar C-C ( cm -1 ), ν C=O (1735 cm -1 ), ν N-H + ( cm -1 ), ν al С-Н ( cm -1 ), ar С-Н (3068 cm -1 ), С-Н bonds of heterocycles (3129 cm -1 ) [36]. 1 H NMR (DMSO-d 6 ): (CH 3 -), 1.43 (CH 3 -C), (-CH 2 -), (-CCH 2 OCH 2 CH 2 OC(O)-), (-CH 2 OC(O)-), (-Ar-H, - NH=CH-NH-). 13 C NMR (CDCl 3 ): (CH 3 -CH 2 -), (CH 3 -C-), (CH 3 -CH 2 - CH 2 -), 23.89, 26.84, 29.39, 29.74, 31.95, (-CH 2 -CH 2 -CH 2 -), (-C(O)-NH-CH 2 - CH 2 -), 46.61, (-C(CH 3 )(CH 2 -)), (-C-CH 2 -O-), 88.95, , , , , (-C=C-C=, -NH-CH=CH-), , (-C=O). The STr 16 is abbreviations for this type of HBP-IL.

5 S5 Figure S1. 1 Н NMR spectrum of CTr 16 HBP-ILs. Figure S2. 1 Н NMR spectrum of SIm 16 HBP-ILs.

6 Figure S3. 1 Н NMR spectrum of STr 16 HBP-ILs. S6

7 Figure S4. Molecular model of HBP-OH core (a) and CIm 16 (b), STr 16 (c) HBP-ILs. S7

8 S8 Table S1. Thermal behaviour of effective size of HBP-IL assemblies in aqueous media at ph 5.2. Sample M n,theory (g/mol) Size (nm) 25 C 30 C 40 C CIm ±50 168±53 172±49 CTr ±60 209±55 220±64 SIm ±10 29±10 33±11 STr ±10 35±9 38±10

9 Figure S5. TEM images of the CTr 16 (a), SIm 16 (b) and STr 16 (c) HBP-ILs assemblies deposited from ph 5.2 solutions on carbon-formvar-coated copper grids. Scale bar is 200 nm. S9