SUPPLEMENTARY INFORMATION

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1 SUPPLEMENTARY INFORMATION Supplementary Information Macroscopic self-assembly through molecular recognition Akira Harada,* Ryosuke Kobayashi, Yoshinori Takashima, Akihito Hashidzume & Hiroyasu Yamaguchi Department of Macromolecular Science, Graduate School of Science, Osaka University, Toyonaka, Osaka , Japan Japan Science and Technology Agency (JST), Core Research for Evolutional Science and Technology (CREST), 5 Sanbancho, Chiyoda-ku, Tokyo , Japan. *To whom correspondence should be addressed. harada@chem.sci.osaka-u.ac.jp (A.H.) nature chemistry 1

2 Page Content S5 Materials and measurements. S7 Preparation of host monomers (6-acrylamido-α-CD and 6-acrylamido-β-CD). S9 Figure S1. 1 H NMR spectra of 6-acrylamido-α-CD and 6-acrylamido-β-CD in DMSO-d 6. S10 Preparation of adamantantyl (Ad) acrylamide. S11 Figure S2. 1 H NMR spectra of Ad acrylamide in DMSO-d 6. S12 Preparation of host gels. Figure S3. 1 H NMR spectra of host gels (α-cd-gel and β-cd-gel) in DMSO-d 6. S13 Figure S4. IR spectra of host gels (α-cd-gel and β-cd-gel) using the KBr pellet. S14 Preparation of guest gels. S15 Figure S5. 1 H NMR spectra of guest gels (Ad-gel, t-bu-gel, n-bu-gel) in DMSO-d 6. Figure S6. IR spectra of guest gels (Ad-gel, t-bu-gel, n-bu-gel) using the KBr pellet. S16 Determination of apparent association constants of the complexes of CDs with model guest polymers. S17 Table S1. Apparent association constants (K a ) for CDs with model guest polymers (Ad-PA, t-bu-pa, and n-bu-pa). S18 Figure S7. 1 HNMR spectra for Ad-PA(1mM in guest unit) in the absence of CDs (A) and in the presence of -CD in 2 mm (B), 4 mm (C), 6 mm (D), 8 mm (E), and 10mM (F). S19 Figure S8. Benesi Hildebrand plots of 1/Δδ obs against 1/C CD. S20 Table S2. Properties of macroscopic self-assemblies between host-gel and guest-gel. 2 nature chemistry

3 S21 Figure S9. Adhesion intensities of macroscopic self-assemblies between host-gel and guestgel determined by mechanical tension testing. [Note] The movie files of the macroscopic self-assemblies between host-gels and guest-gels are uploaded in Supporting Information. Movie S1. A β-cd-gel (red gel) was brought in contact with a Ad-gel (green gel). β-cd-gel adhered so firmly to Ad-gel. Movie S2. Macroscopic self-assembly between β-cd-gel (red gels) and Ad-gel (green gels) placed in a Petri dish. Adding of 5 ml of water and shaking a few min led to the selective formation of an alternating self-assembly between β-cd-gel (red gels) and Ad-gel (green gels). Movie S3. Macroscopic self-assembly between α-cd-gel (blue gels) and guest gels (n-bu-gel (yellow gels) and t-bu-gel (green gels)) placed in a Petri dish. Adding of 5 ml of water and shaking a few min led to the selective formation of an alternating self-assembly between α-cd-gel (blue gels) and n-bu-gel (yellow gel). Movie S4. Macroscopic self-assembly between host-gel (β-cd-gel (red gels)) and guest gels (n-bu-gel (yellow gels) and t-bu-gel (green gels)) placed in a Petri dish. Adding of 5 ml of water at shaking a few min led to the selective formation of an alternating self-assembly between β- CD-gel (red gels) and t-bu-gel (green gels). nature chemistry 3

4 Movie S5. Macroscopic self-assembly between host gels (α-cd-gel (blue gels) and β-cd-gel (red gels)) and guest gels (n-bu-gel (yellow gels) and t-bu-gel (green gels)) placed in a Petri dish. Adding of 5 ml of water at shaking a few min led to the selective formation of an alternating self-assemblies of α-cd-gel/n-bu-gel and β-cd-gel/t-bu-gel. 4 nature chemistry

5 Materials α-cyclodextrin (α-cd) and β-cd were obtained from Junsei Chemical Co., Ltd. NaHCO 3, NaOH, acetone, methanol, 1-adamantylamine, triethylamine, THF, chloroform, 2,2'-azobis(isobutyronitrile), Dimethyl sulfoxide, ammonium peroxodisulfate (APS), N,N,N',N'-tetramethylethylenediamine (TMEDA), N,N'-methylenebis(acrylamide) and acrylamide were obtained from Nacalai Tesque Inc. Acryloyl chloride was obtained from Wako Pure Chemical Industries, Ltd. t-butyl acrylate and n-butyl acrylate were obtained from Tokyo Kasei Co., Ltd. CDs were recrystallized twice from distilled water. The other materials were used without further purification. Measurements 1 H-NMR spectra were recorded at 500 MHz with a JEOL ECA-500 NMR spectrometer. Chemical shifts were referenced to the solvent values ( 2.49 ppm for DMSO, 4.79 ppm for HOD, and 7.25 ppm for CDCl 3 ). IR spectra were recorded with a JASCO FT-IR-410 spectrometer. Mechanical properties of contacted with host gel and guest gel was measured by the mechanical tension testing system (Rheoner, RE-33005, Yamaden Ltd.). Host-gel and guest-gels were pushed together to contact with each other. The samples of 1 1 cm length were measured with a speed of 0.1 mm/sec at room temperature. nature chemistry 5

6 Self-assembly of host-gels/guest-gels Macroscopic self-assembly between host gels and guest gels was performed in water. Pieces of -CD-gel, -CD-gel, n-bu-gel, and t-bu-gel were stained by soaking these gels into the solutions of blue-, red-, yellow-, and green-dyes, respectively. Ad-gel (light green) was also colored in the same way. Each gel was placed in a Petri dish, followed by adding 5 ml of water and shaking (EYELA CM- 1000) for a few minutes at room temperature. 6 nature chemistry

7 Preparation of host monomers (acrylamido-α-cd and acrylamido-β-cd) (i) 6-Acrylamido-α-CD 6-Amino-α-CD (580mg 0.60mmol) was dissolved in 50 ml of NaHCO 3 aq. (0.50 g) and ph of the solution was adjusted to around 10 with NaOH. Acryloyl chloride (90 l, 1.2 mmol) was added to the solution of 6-amino-α-CD on ice bath. The solution was stirred for 6 hours on ice bath. After the prescribed time, the solution was evaporated to 10% of the total volume and poured into acetone (500 ml). The precipitate was collected by centrifugation, and then dried with vacuum oven for an overnight. The crude product was purified by reversed phase chromatography using HP-20 polystyrene gel (methanol/water) to give 6-acrylamido-α-CD (0.49 g, 79%). 1 H NMR (500MHz, DMSO-d 6 ): 8.00 (t, 1H, amide), 6.27 (dd, 1H, olefin), 6.02 (d, 1H, olefin), (d, 1H, olefin and m, 13H, O 2,3 H of CD) (m, 6H C 1 H of CD), (m, 5H, O 6 H of CD), (m, overlaps with HOD). MALDI-TOF MS; m/z = ([C 39 H 63 NO 30 + Na] + = ), ([C 39 H 63 NO 30 + K] + = ). Elemental Anal. Calcd for C 39 H 63 NO 30 (H 2 O) 6 : C, 41.31; H, 6.67; N,1.24. Found: C, 41.24; H, 6.36; N, (ii) 6-Acrylamido-β-CD 6-Amino- -CD (0.68 g 0.60 mmol) was dissolved in 50 ml of NaHCO 3 aq. (0.50 g) and ph of the solution was adjusted to around 10 with NaOH. Acryloyl chloride (90 l, 1.2 mmol) was added to the solution of 6-amino-β-CD on ice bath. The solution was stirred for 6 hours on ice bath. After the prescribed time, the solution was evaporated to 10% of the total volume and nature chemistry 7

8 poured into acetone (500 ml). The precipitate was collected by centrifugation, and then dried with vacuum oven for an overnight. The crude product was purified by reversed phase chromatography using HP-20 polystyrene gel (methanol/water) to give 6-acrylamido-α-CD (0.53 g, 74%). 1 H NMR (500 MHz, DMSO-d 6 ): 7.90 (t, 1H, amide), 6.27 (dd, 1H, olefin), 6.02 (d, 1H, olefin), (d, 1H, olefin and m, 15H, O 2,3 H of CD) (m, 7H, C 1 H of CD), (m, 6H, O 6 H of CD), (m, overlaps with HOD). MALDI-TOF MS; m/z = ([C 45 H 73 NO 35 +Na] + = ), ([C 45 H 73 NO 35 +K] + = ). Elemental Anal. Calcd for C 45 H 73 NO 35 (H 2 O) 3.32 : C, 41.54; H, 6.17; N,1.07. Found: C, 41.54; H, 6.37; N, nature chemistry

9 Figure S MHz 1 H NMR spectra of 6-acrylamido-α-CD (a) and 6-acrylamido-β-CD (b) in DMSOd 6 at 30 o C. nature chemistry 9

10 Preparation of adamantyl (Ad) acrylamide. 1-Adamantylamine (0.76 g, 5.0 mmol) and triethylamine (770 l, 5.5 mmol) was dissolved in 40 ml of dried THF on ice bath. Acryloyl chloride was added to the solution of 1-adamantylamine (450 l, 5.5 mmol) on ice bath. The solution was stirred for 4 hours on ice bath. The precipitate was removed by the filtration, and the supernatant was concentrated under the reduced pressure. The obtained crude product was purified by a recrystalization from chloroform (0.85 mg, 83%). 1 H NMR (500 MHz, (CD 3 ) 2 SO): dd, 1H, olefin 5.96 (dd, 1H, olefin), 5.56 (dd, 1H, olefin), 5.15 (brs, 1H, NH), 2.06 (m, 9H, adamantane), 1.59 (m, 6H, adamantane). MALDI-TOF MS ; m/z = ([C 13 H 19 NO+Na] + =228.1), ([C 13 H 19 NO+K] + =244.1). Elemental Anal. Calcd for C 13 H 19 NO(H 2 O) 0.16 : C, 74.09; H, 9.24; N,6.64. Found: C, 74.06; H, 9.18; N, nature chemistry

11 Figure S2. 1 H NMR spectra of Ad acrylamide in DMSO-d 6 nature chemistry 11

12 Preparation of host gels. A soluble host polymer containing -CD was prepared by copolymerization of acrylamide and 6-acrylamido- -CD (2 mol%) by radical polymerization initiated by a redox pair of ammonium peroxodisulfate (APS) and N,N,N',N'-tetramethylethylenediamine (TMEDA) in water. The molecular weight was estimated to be by viscometry using formamide as a solvent. -CD-gel was prepared by copolymerization of acrylamide (6.2 mmol), 6-acrylamido- -CD (0.31 mmol) and N,N'-methylenebis(acrylamide) (0.03 mmol) by radical polymerization initiated by a redox pair of APS and TMEDA in water. -CD-gel was also prepared in a similar way. (a) (b) Figure S3. 1 H NMR spectra of host gels (α-cd-gel (a) and β-cd gel (b)) in DMSO-d nature chemistry

13 Figure S4. IR spectra of host gels (α-cd-gel (black) and β-cd-gel (red)) using the KBr pellet. nature chemistry 13

14 Preparation of guest gels. A soluble guest polymer bearing adamantyl (Ad) groups was prepared by copolymerization of acrylamide (31 mmol) and N-(1-adamantylamide) (0.62 mmol) by a radial polymerization using 2,2'- azobis(isobutyronitrile) (AIBN) (0.04 mmol) in dimethyl sulfoxide (DMSO) at 60 C. Ad-gel was prepared by copolymerization of acrylamide (6.2 mmol), N-(1- adamantyl)acrylamide (0.32 mmol), and N,N'-methylenebis(acrylamide) (0.12 mmol) by radical polymerization using AIBN (0.03 mmol) in DMSO at 63 C. The gels were purified by exposing water several hours and then repeated washing with water. 14 nature chemistry

15 (a) (b) (c) Figure S5. 1 H NMR spectra of guest-gels (Ad-gel (a), t-bu-gel (b), n-bu-gel (c)) in DMSO-d 6. Figure S6. IR spectra of guest gels (Ad-gel (blue line), t-bu-gel (red line), n-bu-gel (green line)) using the KBr pellet. nature chemistry 15

16 Determination of Apparent Association Constants of the complexes of CDs with Model Guest Polymers. Before the study on the macroscopic self-assembly, we investigated the interaction of CDs with model guest polymers (Ad-PA, t-bu-pa, and n-bu-pa) bearing adamantyl (Ad), t-butyl (t-bu), and n- butyl groups (n-bu) by 1 H NMR to estimate apparent association constants (K a ). Figure S7 shows a typical example of the 1 H NMR spectra for Ad-PA in the presence of varying concentrations of -CD (C CD ). As C CD is increased, clear down-field shifts and broadening of the signals due to protons in Ad group were observed, indicative of the interaction of -CD with Ad group. Using the 1 H NMR spectra, the reciprocals of the peak shifts for the signal due to the protons in the Ad group at 1.37 ppm (1/ obs ) were calculated and plotted against the reciprocals of the CD concentrations (1/C CD ). As can be seen in Figure S8, the plots show a good linear relationship, indicating that the interaction of -CD with Ad group can be analyzed based on the formation of one-to-one complexes. From the intercept and the slope of the straight line, the apparent K a value was determined to be M -1 by 1 obs 1 1 Ka C CD 1 (1) where is the difference between the observed chemical shift for the one-to-one complex of -CD with the Ad group and the chemical shift in the absence of -CD. Figure S8 also includes data for other pairs of CDs and model guest polymers. As can be seen in this figure, plots demonstrate good linear relationships for all the pairs. From the intercepts and the slopes of the straight lines, the apparent K a values were also determined, as listed in Table S1. 16 nature chemistry

17 Table S1. Apparent association constants (K a ) for CDs with model guest polymers (Ad-PA, t-bu-pa, and n-bu-pa). Model guest polymers K a / M 1 a -CD -CD Ad-PA t-bu-pa n-bu-pa 57 <10 b a. Determined by 1 H NMR. b. No peak shifts was observed. nature chemistry 17

18 (F) (E) (D) (C) (B) (A) / ppm Figure S7. 1 HNMR spectra for Ad-PA(1mM in guest unit) in the absence of CDs (A) and in the presence of -CD in 2 mm (B), 4 mm (C), 6 mm (D), 8 mm (E), and 10 mm (F). 18 nature chemistry

19 Figure S8. Benesi Hildebrand plots of 1/Δδ obs against 1/C CD. nature chemistry 19

20 Table S2. Properties of macroscopic self-assemblies between host-gel and guest-gel. Host gel Guest gel Assembly a Stress / Pa b Strain / % b K a / M -1 c α-cd-gel Ad-gel A 900±150 75±10 98 α-cd-gel n-bu-gel A ±50 ± 57 α-cd-gel t-bu-gel N 15 β-cd-gel Ad-gel sa 1050 ±150 d 87± β-cd-gel n-bu-gel N <10 β-cd-gel t-bu-gel A ±100 ±4 170 α-cd-gel 3500±200 85±5 β-cd-gel 8700±200 23±6 Ad-gel 1400± ±10 t-bu-gel 1550±150 70±10 n-bu-gel 3050±150 50±8 a Interactions between host gels and guest gels; strongly aggregated (sa) difficult to separate, aggregated (A), no interactions (N) were observed in water or in humid air. Host/guest interactions were tested at least three times. b Physical properties of host-gels and guest-gels by materials tension testing machines. The stress and strain were measured twice and these data were shown as the averages with standard deviations. c Association constants (K a ) were determined by Benesi-Hildebrand plots of the chemical shifts of the peaks in the 1 H NMR spectra of soluble guest polymers with CDs. d The part of Ad-gel in β-cd-gel/ad-gel was broken without damaging the contact interface during the materials tension testing. 20 nature chemistry

21 Figure S9. Adhesion intensities of macroscopic self-assemblies between host-gel and guest-gel determined by mechanical tension testing. The part of Ad-gel in β-cd-gel/ad-gel was broken during the materials tension testing. nature chemistry 21