Supporting Information. Supramolecular materials crosslinked by host. guest inclusion complexes: the effect of side chain

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1 Supporting Information Supramolecular materials crosslinked by host guest inclusion complexes: the effect of side chain molecules on mechanical properties Yoshinori Takashima 1, Yuki Sawa 1, Kazuhisa Iwaso 1, Masaki Nakahata 1, Hiroyasu Yamaguchi 1, Akira Harada 1,2 * CONTENTS 1. Experimental details 2. Preparation of 6 acrylamido methylether αcd (αcdaamme) 3. Preparation of 6 acrylamido methylether βcd (βcdaamme) 4. Preparation of gels 5. Characterization of gels 6. Association constants between CDAAm and guest monomers 7. Mechanical property of hydrogels 8. Self-healing efficiency References S1

2 1. Experimental details Materials. Acrylamide (AAm), N-(hydroxylmethyl)acrylamide (AAmMe), n-butyl acrylate (Bu), n-hexyl acrylate (Hex), and N,N,N',N' tetramethylethylenediamine (TEMED) were purchased from Tokyo Chemical Industry Co., Ltd. n-dodecyl acrylate (Dod), CDCl3, and D2O were purchased from Wako Pure Chemical Industries, Ltd. αcyclodextrin (αcd) and βcyclodextrin (βcd) were obtained from Junsei Chemical Co. Ltd. p-toluenesulfonic acid monohydrate, ammonium peroxodisulfate (APS), and N,N' methylenebis(acrylamide) (MBAAm) were purchased from Nacalai Tesque Inc. Methoxy triethylene glycol acrylate (TEGA), isobornyl acrylate (Ibr), 3-hydroxy-1-adamantyl acrylate (HAdA), and 2-ethyl-2- adamanthyl acrylate (EtAdA) were obtained from Kyoeisha Chemical Co. Ltd. DMSO d6 was obtained from Merck & Co., Inc. Water used for the preparation of the aqueous solutions was purified with a Millipore Elix 5 system. Other reagents were used without further purification. 6 Acrylamido αcd (αcdaam), 6 acrylamido βcd (βcdaam), and adamantane-acrylamide (Ad-AAm) were prepared according to our previous reports and reference. 1,2,3 S2

3 Measurements. 1 H and 13 C NMR spectra were recorded at 500 MHz with a JEOL JNM ECA 500 NMR spectrometer. Solid state 1 H field gradient magic angle spinning (FGMAS) NMR spectra were recorded at 400 MHz with a JEOL JNM ECA 400 NMR spectrometer. Sample spinning rate was 7 khz. In all NMR measurements, chemical shifts were referenced to the solvent values (δ = 2.49 ppm, and 4.79 ppm for DMSO d6, and D2O, respectively). FT-IR spectra were measured using a JASCO FT/IR 410 spectrometer. Positive ion matrix assisted laser desorption/ionization time of flight mass spectrometry (MALDI TOF MS) experiments were performed using a Bruker autoflex speed mass spectrometer using 2,5 dihydroxy benzoic acid as a matrix. Mass number was calibrated by four peptides, i.e., angiotensin II ([M+H] ), angiotensin I ([M+H] ), substance P ([M+H] ), and bombesin ([M+H] ). Mechanical properties of the gels were measured by Autograph AG-X plus (Shimadzu Co.). Purification of CDAAm are performed using a Waters HPLC with SunFire C18 OBD Prep Column. S3

4 2. Preparation of 6 acrylamido methylether αcd (αcdaamme) Scheme S1. Preparation of αcdaamme [Procedure] α-cd (20g 21mmol) and N-(hydroxymethyl)acrylamide (2.0g 20mmol) were dissolved in 100mL of DMF. p-toluenesulfonic acid monohydrate (500mg 2.6mmol) was added to the solution. The solution was stirred for 1 hour at 80 degrees on oil bath. After the prescribed time, the solution was poured into 500mL of acetone. The precipitate was filtered and washed with 30mL of acetone three times. The residue was dried with vacuum oven for an overnight. The clude product was purified by high performance liquid chromatography using ODS column to give αcdaamme (2.39g, 11%). MALDI-TOF MS; m/z =1078.5, ([C46H75NO36 +Na] + = ), ([C46H75NO36+K] + = ). Figure S1. 1 H NMR spectrum of αcdaamme Figure S2. 13 C NMR spectrum of αcdaamme S4

5 3. Preparation of 6 acrylamido methylether βcd (βcdaamme) Scheme S2. Preparation of βcdaamme [Procedure] β-cd (15g 13mmol) and N-(hydroxymethyl)acrylamide (2.0g 20mmol) were dissolved in 100mL of DMF. p-toluenesulfonic acid monohydrate (500mg 2.6mmol) was added to the solution. The solution was stirred for an half hour at 80 degrees on oil bath. After the prescribed time, the solution was poured into 500mL of acetone. The precipitate was filtered and washed with 30mL of acetone three times. The residue was dried with vacuum oven for an overnight. The clude product was purified by high performance liquid chromatography using ODS column to give βcdaamme (2.90g, 18%). MALDI-TOF MS; m/z =1240.6, ([C46H75NO36 +Na] + = ), ([C46H75NO36+K] + = ). Figure S3. 1 H NMR spectrum of βcdaamme Figure S4. 13 C NMR spectrum of βcdaamme S5

6 4. Preparation of gels [Typical procedure] First, host monomer (βcdaamme) and guest monomers (AdAAm) were mixed in water. Heating the suspension resulted in transparent solution, indicating formation of inclusion complexes between host and guest monomers. These inclusion complexes were copolymerized with main chain monomer (AAm, or TEGA) initiated by a combination of ammonium persulfate (APS) and N,N,N,N -tetramethylethylenediamine (TEMED). Here x and y represent the mol% of CDAAmMe and guest units. Scheme S3. Preparation of βcdaamme-adaam hydrogel (x,y). S6

7 Table S1. Polymerization feed ratio of αcdaamme and Bu togive αcdaamme-bu hydrogel. cross-linking n-buthyl αcdaamme ratio acrylate AAm APS TEMED H 2 O 1mol% 21.1mg 2.9μL 139.3mg 4.6mg 3μL 1mL 2mol% 42.2mg 5.8μL 136.5mg 4.6mg 3μL 1mL 3mol% 63.4mg 8.7μL 133.6mg 4.6mg 3μL 1mL Table S2. Polymerization feed ratio of αcdaamme and Hex togive αcdaamme-hex hydrogel. cross-linking n-hexyl αcdaamme ratio acrylate AAm APS TEMED H 2 O 1mol% 21.1mg 3.5μL 139.3mg 4.6mg 3μL 1mL 2mol% 42.2mg 7.0μL 136.5mg 4.6mg 3μL 1mL 3mol% 63.4mg 10.6μL 133.6mg 4.6mg 3μL 1mL Table S3. Polymerization feed ratio of αcdaamme and Dod togive αcdaamme-dod hydrogel. cross-linking n-dodecyl αcdaamme ratio acrylate AAm APS TEMED H 2 O 1mol% 21.1mg 5.5μL 139.3mg 4.6mg 3μL 1mL 2mol% 42.2mg 11.0μL 136.5mg 4.6mg 3μL 1mL 3mol% 63.4mg 16.5μL 133.6mg 4.6mg 3μL 1mL Table S4. Polymerization feed ratio of βcdaamme and Ibr togive βcdaamme-ibr hydrogel. cross-linking ratio βcdaamme Ibr AAm APS TEMED H 2 O 1mol% 24.4mg 4.2μL 139.3mg 4.6mg 3μL 1mL 2mol% 48.7mg 8.3μL 136.5mg 4.6mg 3μL 1mL 3mol% 73.1mg 12.5μL 133.6mg 4.6mg 3μL 1mL Table S5. Polymerization feed ratio of βcdaamme and AdAAm togive βcdaamme- AdAAm hydrogel. cross-linking ratio βcdaamme AdAAm AAm APS TEMED H 2 O 1mol% 24.4mg 4.1mg 139.3mg 4.6mg 3μL 1mL 2mol% 48.7mg 8.2mg 136.5mg 4.6mg 3μL 1mL 3mol% 73.1mg 12.3mg 133.6mg 4.6mg 3μL 1mL Table S6. Polymerization feed ratio of βcdaamme and HAdA togive βcdaamme-hada hydrogel. cross-linking ratio βcdaamme HAdA AAm APS TEMED H 2 O 1mol% 24.4mg 4.4mg 139.3mg 4.6mg 3μL 1mL 2mol% 48.7mg 8.9mg 136.5mg 4.6mg 3μL 1mL 3mol% 73.1mg 13.3mg 133.6mg 4.6mg 3μL 1mL S7

8 Table S7. Polymerization feed ratio of βcdaamme and EtAdA togive βcdaamme- EtAdA hydrogel. cross-linking ratio βcdaamme EtAdA AAm APS TEMED H 2 O 1mol% 24.4mg 4.7μL 139.3mg 4.6mg 3μL 1mL 2mol% 48.7mg 9.4μL 136.5mg 4.6mg 3μL 1mL 3mol% 73.1mg 14.1μL 133.6mg 4.6mg 3μL 1mL Table S8. Polymerization feed ratio of βcdaamme and Ibr togive βcdaamme-ibr xerorogel. cross-linking ratio βcdaamme Ibr TEGA APS TEMED H 2 O 1mol% 24.4mg 4.2μL 396.1μL 4.6mg 3μL 1mL 2mol% 48.7mg 8.3μL 388.0μL 4.6mg 3μL 1mL 3mol% 73.1mg 12.5μL 379.9μL 4.6mg 3μL 1mL Table S9. Polymerization feed ratio of βcdaamme and AdAAm togive βcdaamme- AdAAm xerogel. cross-linking ratio βcdaamme AdAAm TEGA APS TEMED H 2 O 1mol% 24.4mg 4.1mg 396.1μL 4.6mg 3μL 1mL 2mol% 48.7mg 8.2mg 388.0μL 4.6mg 3μL 1mL 3mol% 73.1mg 12.3mg 379.9μL 4.6mg 3μL 1mL Table S10. Polymerization feed ratio of βcdaamme and AdEtA togive βcdaamme- AdEtA xerogel. cross-linking ratio βcdaamme HAdA TEGA APS TEMED H 2 O 1mol% 24.4mg 4.4mg 396.1μL 4.6mg 3μL 1mL 2mol% 48.7mg 8.9mg 388.0μL 4.6mg 3μL 1mL 3mol% 73.1mg 13.3mg 379.9μL 4.6mg 3μL 1mL Table S11. Polymerization feed ratio of βcdaamme and EtAdA togive βcdaamme- EtAdA xerogel. cross-linking ratio βcdaamme EtAdA TEGA APS TEMED H 2 O 1mol% 24.4mg 4.7μL 396.1μL 4.6mg 3μL 1mL 2mol% 48.7mg 9.4μL 388.0μL 4.6mg 3μL 1mL 3mol% 73.1mg 14.1μL 379.9μL 4.6mg 3μL 1mL Table S12. Polymerization feed ratio of AAm and MBAAm togive AAm hydrogel. cross-linking ratio AAm MBAAm APS TEMED H 2 O 1mol% 140.7mg 3.1mg 4.6mg 3μL 1mL 2mol% 139.3mg 6.2mg 4.6mg 3μL 1mL 3mol% 379.9μL 9.3mg 4.6mg 3μL 1mL S8

9 Table S13. Polymerization feed ratio of TEGA and MBAAm togive TEGA xerogel. cross-linking ratio TEGA MBAAm APS TEMED H 2 O 1mol% 396.1μL 3.1mg 4.6mg 3μL 1mL 2mol% 388.0μL 6.2mg 4.6mg 3μL 1mL 3mol% 379.9μL 9.3mg 4.6mg 3μL 1mL S9

10 5. Characterization of gels FGMAS NMR measurement. Figure S5. Solid-state 1 H FGMAS NMR spectra of αcdaamme-bu hydrogel (2,2). (Immersed in D2O, 400 MHz, 30 C, rotation frequency = 7 khz) Figure S6. Solid-state 1 H FGMAS NMR spectra of αcdaamme-hex hydrogel (2,2). (Immersed in D2O, 400 MHz, 30 C, rotation frequency = 7 khz) S10

11 Figure S7. Solid-state 1 H FGMAS NMR spectra of αcdaamme-dod hydrogel (2,2). (Immersed in D2O, 400 MHz, 30 C, rotation frequency = 7 khz) S11

12 Figure S8. Solid-state 1 H FGMAS NMR spectra of βcdaamme-ibr hydrogel (2,2). (Immersed in D2O, 400 MHz, 30 C, rotation frequency = 7 khz) Figure S9. Solid-state 1 H FGMAS NMR spectra of βcdaamme-adaam hydrogel (2,2). (Immersed in D2O, 400 MHz, 30 C, rotation frequency = 7 khz) S12

13 Figure S10. Solid-state 1 H FGMAS NMR spectra of βcdaamme-hada hydrogel (2,2). (Immersed in D2O, 400 MHz, 30 C, rotation frequency = 7 khz) Figure S11. Solid-state 1 H FGMAS NMR spectra of βcdaamme-etada hydrogel (2,2). (Immersed in D2O, 400 MHz, 30 C, rotation frequency = 7 khz) S13

14 Figure S12. Solid-state 1 H FGMAS NMR spectra of βcdaamme-ibr xerorogel (2,2). (Immersed in D2O, 400 MHz, 30 C, rotation frequency = 7 khz) Figure S13. Solid-state 1 H FGMAS NMR spectra of βcdaamme-adaam xerogel (2,2). (Immersed in D2O, 400 MHz, 30 C, rotation frequency = 7 khz) S14

15 Figure S14. Solid-state 1 H FGMAS NMR spectra of βcdaamme-hada(2,2) xerogel. (Immersed in D2O, 400 MHz, 30 C, rotation frequency = 7 khz) Figure S15. Solid-state 1 H FGMAS NMR spectra of βcdaamme-etada(2,2) xerogel. (Immersed in D2O, 400 MHz, 30 C, rotation frequency = 7 khz) S15

16 FT-IR measurement. Figure S16. FT IR spectrum of αcdaamme-bu hydrogel (2,2), αcdaamme-hex hydrogel (2,2), and αcdaamme-dod hydrogel (2,2). (ATR, r.t.) S16

17 S17

18 Figure S17. FT IR spectrum of βcdaamme-ibr hydrogel (2,2),βCDAAmMe-AdAAm hydrogel (2,2), βcdaamme-hada hydrogel (2,2), βcdaamme-etada hydrogel (2,2), AAm hydrogel (2),. (ATR, r.t.) S18

19 6. Association constants between CDAAm and guest monomers Table S14. Association constants between αcdaamme and guest monomers Bu Hex Dod Association constants / M Table S15. Association constants between βcdaamme and guest monomers Ibr AdAAm HAdA EtAdA Association constants / M S19

20 7. Mechanical property of hydrogels Figure S18. Stress-strain curves of αcdaamme-bu hydrogel (1,1), αcdaamme-bu hydrogel (2,2), and αcdaamme-bu hydrogel (3,3), prepared at Cm = 2 mol/kg, respectively. Figure S19. Stress-strain curves of αcdaamme-hex hydrogel (1,1), αcdaamme-hex hydrogel (2,2), and αcdaamme-hex hydrogel (3,3), prepared at Cm = 2 mol/kg, respectively. S20

21 Figure S20. Stress-strain curves of αcdaamme-dod hydrogel (1,1), αcdaamme-dod hydrogel (2,2), and αcdaamme-dod hydrogel (3,3), prepared at Cm = 2 mol/kg, respectively. S21

22 Figure S21. Stress-strain curves of βcdaamme-ibr hydrogel (1,1), βcdaamme-ibr hydrogel (2,2), and βcdaamme-ibr hydrogel (3,3), prepared at Cm = 2 mol/kg, respectively. Figure S22. Stress-strain curves of βcdaamme-adaam hydrogel (1,1), βcdaamme- AdAAm hydrogel (2,2), and βcdaamme-adaam hydrogel (3,3), prepared at Cm = 2 mol/kg, respectively. S22

23 Figure S23. Stress-strain curves of βcdaamme-hada hydrogel (1,1), βcdaamme-hada hydrogel (2,2), and βcdaamme-hada hydrogel (3,3), prepared at Cm = 2 mol/kg, respectively. Figure S24. Stress-strain curves of βcdaamme-etada hydrogel (1,1), βcdaamme- EtAdA hydrogel (2,2), and βcdaamme-etada hydrogel (3,3), prepared at Cm = 2 mol/kg, respectively. S23

24 8. Self-healing efficiency Figure S25. Normalized stress-strain curves of βcdaam-ibr TEGA xerogel (2,2) (Cm = 2 mol/kg) before and after self-healing for 2 day and 5 days at room temperature. After 5 days, self-healing efficiency reach to about 13% of the original material strength. Figure S26. Normalized stress-strain curves of βcdaam-adaam TEGA xerogel (2,2) (Cm = 2 mol/kg) before and after self-healing for 2 day and 5 days at room temperature. After 5 days, self-healing efficiency reach to about 35% of the original material strength. S24

25 Figure S27. Normalized stress-strain curves of βcdaam-hada TEGA xerogel (2,2) (Cm = 2 mol/kg) before and after self-healing for 2 day and 5 days at room temperature. After 5 days, self-healing efficiency reach to about 29% of the original material strength. Figure S28. Normalized stress-strain curves of βcdaam-etada TEGA xerogel (2,2) (Cm = 2 mol/kg) before and after self-healing for 2 day and 5 days at room temperature. After 5 days, self-healing efficiency reach to about 21% of the original material strength. S25

26 Figure S29. The rupture stress (a) and strain (b) of the αcdaamme-r hydrogels(m, n) (αcdaamme-nbu, αcdaamme-hex, and αcdaamme-dod hydrogels). S26

27 Figure S30. The rupture stress (a) and strain (b) of the βcdaamme-r hydrogels(m, n) (βcdaamme-ibr, βcdaamme-adaam, βcdaamme-hada, and βcdaamme-adeta hydrogels). Additionally, the association constants of βcd with the spherical alkyl guest groups are described in the figure. S27

28 Figure S31. Evaluation procedure of the self-healing properties of xerogels. First the xerogel dried in air is carried out a tensile test to determine the initial stress strength (S0). Next another xerogel is cut at the center of the gel using a razor. The two gels are then rejoined and allowed to sit for a certain period before the adhesion strength (S1) on the joint surface is determined. Self-healing ratio of the adhesive strength defined S1/S0. S28

29 References [1] T. Kakuta, Y. Takashima, M. Nakahata, M. Otsubo, H. Yamaguchi, A. Harada, Adv. Mater. 2013, 25, [2] M. Nakahata, Y. Takashima, A. Hashidzume, A. Harada, Angew. Chem. Int. Ed. 2013, 52, [3] P. Dutta, J. Dey, A. Shome, P. K. Das, Int. J. Pharm. 2011, 414, [4] Hashidzume, A.; Harada, A. Polym. Chem. 2011, 2, S29