1 Supporting Information. 2 Adhesive RAFT Agents for Controlled Polymerization of Acrylamide: Effect of. 3 Catechol-end R Groups

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1 Electronic upplementary Material (EI) for RC Advances. This journal is The Royal ociety of Chemistry 0 upporting Information Adhesive RAFT Agents for Controlled Polymerization of Acrylamide: Effect of Catechol-end R Groups 4 labode. yeneye, William Z. Xu, Paul A. Charpentier* 5 Department of Chemical and Biochemical Engineering, University of Western ntario, London 6 N N6A-5B9 Canada 7 *Corresponding author: pcharpentier@eng.uwo.ca 8 Experimental ection Complement 9 Characterization: D ( H and C) and D (ghqc, ghmbc) NMR spectra were measured using 0 either a Varian INVA 600 or a Varian INVA 400 spectrometer. ghqc was recorded with multiplicity edited. CDCl, D, or DM-d 6 was used as the solvent and chemical shifts were referenced to tetramethylsilane (TM; 0.0 ppm). The AM concentration [AM] was determined based on the H NMR signals of the olefinic protons. ATR-FTIR spectra were recorded at a 4 resolution of 6 cm - over 64 scans using a mid-ir spectrometer (Nicolet 6700) equipped with smart diamond ATR (attenuated total reflection). UV-Vis spectra were recorded on a himadzu 6 UV-600 (UV-VI-NIR) pectrophotometer equipped with two lamps (halogen and deuterium) 7 and three detectors (photomultiplier tube, InGaAs and cooled Pb) at room temperature. 8 Molecular weight (M n ) and dispersity (Ɖ) of the synthesized PAM samples were measured by a 9 Viscotek GPC Max VE 00 gel permeation chromatography equipped with a triple detector 0 array (TDA 0) including a refractive index detector (RI), a viscometer, and two light scattering detectors (low angle and right angle, 670 nm). 0.0 M NaN/. mm NaN aqueous solution was used as mobile phase at a flow rate of 0.7 ml/min. Two PolyAnalytik columns (A06:

2 0 0 6 Da, 0 Å) were employed to separate the samples at 5 o C, which were calibrated by a 4 polyethylene oxide (PE, MW: 8600 Da, PDI:.0, α = 0.69, K =.7 x 0-4 dl/g) standard. The 5 dn/dc value of PAM in the eluent was pre-determined to be 0. ml/g using a refractometer. 6 The molecular weight averages and dispersities were calculated using mniec software (Ver ). The molecular weight (M n ) of catechol end-functionalized polyacrylamide samples 8 was also determined based on end group analysis of the H NMR spectra of the sample. 9 Thermal properties of the synthesized materials were evaluated via thermogravimetric analysis 0 (TGA) on a DT Q600, TA instruments by heating the materials from room temperature to 700 o C at a heating rate of 0 o C/min under air. A Malvern Zetasizer Nano (Model: ZEN 600) was used to characterize the particle size (P) of the Al -PAM nanocomposites based on dynamic light scattering (DL). The Zetasizer Nano was equipped with a 6 nm He-NE laser 4 source, and at a scattering angle of 7 o. Prior to the P determination which was done in 5 triplicate, the samples were prepared to a concentration of 0 mg/l using distilled water as the 6 dispersion medium (room temperature), and ultra-sonicated for 5 0 min to obtain a well- 7 dispersed suspension.

3 8 upporting Data 9 Table : RAFT Polymerization of acrylamide mediated with Dopa- CTAs Dopa- Time M n, GPC M n, NMR * M w /M n CTA () (min) (a) (b) (c) Reaction conditions: [AM] 0 :[Dopa-CTA] 0 :[ACVA] 0 = 500:5:, 4 olvent = 4.5 ml DM/DMF (97:, vol%), Temp = 70 o C, [AM] 0 = M. 4 *Mn values determined by end-group analysis of the H NMR spectra H a CDCl 0 a Chemical hift (ppm) 4 44 Figure. Complete H NMR spectra of (a) DDMAT (600 5 o C).

4 R a , CDCl R= NH H H a 6 8 CDCl 4-0, R= N 9 8 a 6 CDCl 4 R= H 4 0 5, 8 DM-d6 9 + Cl -7 8 H N H H Chemical hift (ppm) Chemical hift (ppm) 46 Figure. C NMR spectra of (bottom) dopamine hydrochloride, (a) DDMAT, (a) uc-ddmat 47 and (a) Dopa-DDMAT in CDCl (00 5 o C) NH H 4 H F Chemical hift (ppm) 8 H Chemical hift (ppm) 9 49 Figure. ghqc NMR spectrum of Dopa-DDMAT (a) in CDCl (00 5 o C) C Chemical hift (ppm) 4

5 " (b) " 5" 7" " 4" 6" 8" 0" " 0" 9" " " " " CDCl 8" 9" " NH 7" 0" 6" 4" 8" 9" H H ",6" 7" "-9" 4" 0" " " (b) ' 5' 7' ' ' 4' 6' 8' 0' ' 9' ' ' 4' N ' ' 4' CDCl ' 0' ' ' '-9' ' ' (b) CDCl ' H Chemical hift (ppm) 5 Figure 4. H NMR pectra of (b) DoPAT, (b) uc-dopat and (b) Dopa-DoPAT in CDCl ( o C) 5

6 (c) ' (c) ' " CDCl ' " " 4" 6" 8" " 0" 4' 6' 8' 5" 7" 9" 9" 5' 7' 9' 0' ' ' 0" 6" " " N 4" " " N CDCl ' N ' 4' ' 7" " 6" NH 6' 7" 6' ' 8" 9" " 0" " 4" 4" 8" 6' 4' H H " ' " ' "-9" 0" '-9' 0' " ' (c) CDCl N 4 H Chemical hift (ppm) 55 Figure 5. H NMR pectra of (c) CDPA, (c) uc-cdpa and (c) Dopa-CDPA in CDCl ( o C) 6

7 " " " 4" 5" 6" 7" 8" 9" 0" " " " " 6" 4" NH 8" 7" 9" 0" 4" H " " " H CDCl " 4" - 0" (b) " 6" " " 9" 4" 0" 8" " 4" 7" " " " " ' (b) ' ' 4' 5' 6' 7' 8' 9' 7' 0' ' ' ' ' 4' 6' 7' N 8' 7' 8' CDCl ' 4'-0' ' ' 4' 8' ' ' ' ' 6' (b) H CDCl Chemical hift (ppm) 59 Figure 6. C NMR of (b) DoPAT, (b) uc-dopat and (b) Dopa-DoPAT in CDCl ( o C) 7

8 N " " " 4" 6" 8" 0" " " 5" 7" 9" " 6" 4" 8" " 7" 9" NH H 7" 0" " 6" " " 5" H 4" CDCl 4" - 0" " " (c) 5" 6" " " 9" " 6" 7" " 4" 0" 7" " " " N ' (c) ' ' ' 4' 6' 8' 5' 7' 9' 0' ' ' 0' 9' ' 6' 4' 8' 9' 7' N ' 0' 6' 0' ' CDCl ' 4' ' 4' - 0' ' 7' ' 8' ' ' ' ' N (c) H CDCl Chemical hift (ppm) 6 6 Figure 7. C NMR of (c) CDPA, (c) uc-cdpa and (c) Dopa-CDPA in CDCl ( o C) 8

9 R DDMAT_June 4, 0_ATR.esp C-H -H phenol 86 N-H amide 40 C= amide I & C=C aromatic C-N & amide II C= 07 R= NH H H a Absorbance (a.u.) a C= ester 74 C= imide 777 C- ester 0 C- carboxylic acid 80 C= carboxylic acid 70 -H carboxylic acid 90 R= N a R= H Wavenumber (cm-) Wavenumber (cm - ) Figure 8. ATR-FTIR spectra of (a) DDMAT, (a) uc-ddmat and (a) Dopa-DDMAT. Absorbance (a.u.) (c) (b) -H phenol C-H 8 N-H amide 4 C= amide I & C=C aromatic 6-66 C= imide 76 R C= ester 786 C= carboxylic acid 70 C-N & N-H amide II C- ester 00 C- carboxylic acid 06 C= 067 -H 908 R= NH R= N H H (a) R = H Wavenumber (cm - ) 67 Figure 9. ATR-FTIR pectra of (b) DoPAT, (b) uc-dopat and (b) Dopa-DoPAT 9

10 N R Absorbance (a.u.) (c) (b) N-H amide & -H phenol overlaps 86 C-H C= amide I & C=C aromatic C N C= imide 78 C= ester 74 C= carboxylic acid 7 C-N & N-H amide II 9 C- ester 99 C- carboxylic acid 06 C= 066 -H 89 R= NH R= N H H R = H (a) Wavenumber (cm - ) 69 Figure 0. ATR-FTIR pectra of (c) CDPA, (c) uc-cdpa and (c) Dopa-CDPA 0

11 Absorbance (a.u.) wavelength (nm) Figure. UV-vis absorbance spectra of 0.05 mm each of (a, black) DDMAT, (a, red) uc- DDMAT and (a, blue) Dopa-DDMAT in MeH DoPAT uc-dopat Dopa-DoPAT Absorbance (a.u.) wavelength (nm) Figure. UV-vis absorbance spectra of 0.05 mm each of (b, black) DoPAT, uc-dopat (b, CDPA uc-cdpa Dopa-CDPA red) and (b, blue) Dopa-DoPAT in MeH Absorbance (a.u.) wavelength (nm) Figure. UV-vis absorbance spectra of 0.05 mm each of (c, black) CDPA, (c, red) uc- CDPA and (c, blue) Dopa-CDPA in MeH

12 Refractive Index (a) 60 min 0 min 40 min 60 min 60 min Refractive Index (b) 60 min 0 min 40 min 60 min 6 min Retention Volume (ml) Retention Volume (ml) (c) 60 min 0 min 40 min 60 min 60 min Refractive Index Retention Volume (ml) Figure 4: GPC DRI Chromatograms of catechol end-functionalized polyacrylamide (Dopa- PAM) synthesized with (a) Dopa-DDMAT, (b) Dopa-DoPAT and (c) Dopa-CDPA.

13 NH NH 4 7 n H 8 9 H _Bode_PAM_Dopamine_ concentrated.esp D , Chemical hift (ppm) Figure. HNMR spectrum of the synthesized DPAM (4a) in D (600 5 o C)

14 NH NH 4 7 n H 8 9 H C.esp,0,4, 7,,4-, Chemical hift (ppm) Figure 6. C NMR spectrum of the synthesized DPAM (4a) in D (00 5 o C) 4