Synthesis and properties of a dually cleavable graft copolymer comprising pendant acetal linkages

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1 Elctronic upplmntry Mtril (EI) or Polymr Chmistry This ournl is Th Royl ocity o Chmistry 2014 upporting Inormtion ynthsis n proprtis o ully clvl grt copolymr comprising pnnt ctl linkgs K Mio, Wi ho, Hunhun Liu n Youling Zho* Jingsu Ky Lortory o Avnc Functionl Polymr Dsign n Appliction, Dprtmnt o Polymr cinc n Enginring, Collg o Chmistry, Chmicl Enginring n Mtrils cinc, oochow Univrsity, uzhou , Chin Tl 1. Rsults or synthsis o norml (PHP, run 1) n isuli-link (PHP, run 2) poly(hema-co-pegmema) copolymrs y RAFT copolymriztion o HEMA (M 1 ) n PEGMEMA (M 2 ) n norml (CP, runs 3) n isuli-link (CP, run 4) poly(peg-co-pcl) comlik copolymrs y CL polymriztion using vrious mcroinititors (MI) run smpl CTA / MI T ( o C) t (h) C% M n c PDI c M n,nmr DP 1 DP 2 DP PCL w,pcl 1 PHP 4-CPDB PHP -CPDB CP PHP CP PHP Rction conitions: [M 1 ] 0 :[M 2 ] 0 :([CTA] 0 ):[AIBN] 0 = x:x:1:0.2, = 1 (4-CPDB) or 2 (-CPDB), x = 20 (run 1) or 30 (run 2), [M 1 ] 0 = 1.0 mol L 1, in DMF (runs 1 n 2); [CL] 0 :[H] 0 :[n(ct) 2 ] 0 = y:1:0.2, y = 25 (run 3) or 30 (run 4), [CL] 0 = 2.0 mol L 1, in tolun (runs 3 n 4). Totl monomr convrsion trmin y 1 H NMR nlysis. c Numr-vrg molculr wight (g mol 1 ) n polyisprsity stimt y GPC (M n,gpc, runs 1 n 2) or trmin y GPC-MALL (M n,l, runs 3 n 4). Numr-vrg molculr wight (M n,nmr, g mol 1 ) n gr o polymriztion (DP) trmin y 1 H NMR nlysis. Wight prcnt o PCL in copolymr trmin y 1 H NMR nlysis, w,pcl = DP 1 DP PCL /M n,nmr. 1

2 Elctronic upplmntry Mtril (EI) or Polymr Chmistry This ournl is Th Royl ocity o Chmistry 2014 Tl 2. Rsults or synthsis o ci-clvl (ACG) n isuli-link ci-clvl (ACG) poly(peg-co-pcl)-grt-mvpeg grt copolymrs vi uctiv rction twn poly(peg-co-pcl) n MVPEG run smpl prcursor yil M n,th M n,l c PDI c M n,nmr DP 1 DP 2 DP PCL w,pcl 1 ACG CP ACG CP Rction conitions: [MVPEG] 0 :[H] 0 :[PPT] 0 = 2:1:0.2, W polymr :V DMF = 0.30 g ml 1, in DMF t 30 o C or 60 h. Thorticl molculr wight (g mol 1 ), M n,th = M n,nmr (prcursor) + DP 1 M n (MVPEG). c Dtrmin y GPC-MALL. Dtrmin y 1 H NMR nlysis. Polymriztion gr o HEMA (DP 1 ), PEGMEMA (DP 2 ), PCL (DP PCL ) n wight prcnt o PCL in copolymr ( w,pcl ) trmin y 1 H NMR nlysis. PHP PHP Rtntion tim (min) Fig. 1 GPC trcs o PHP n PHP. 2

3 Elctronic upplmntry Mtril (EI) or Polymr Chmistry This ournl is Th Royl ocity o Chmistry 2014 c k l m CN g h H i H i () g h m c,k,l Chmicl shit (ppm) c k l CN H m g h i n p (),h,i g n p m c,k,l Chmicl shit (ppm) Fig. 2 1 H NMR spctr o PHP () n PHP () in DM- 6. 3

4 Elctronic upplmntry Mtril (EI) or Polymr Chmistry This ournl is Th Royl ocity o Chmistry 2014 CN c H g h i H n (),g i c, h Chmicl shit (ppm) g,,k i CN c k i l c H n g h i () l l h Chmicl shit (ppm) Fig. 3 1 H NMR spctr o CP () n ACG () in DM- 6. 4

5 Elctronic upplmntry Mtril (EI) or Polymr Chmistry This ournl is Th Royl ocity o Chmistry 2014 () PHP () PHP (c) CP () CP () ACG () ACG Wvnumr (cm -1 ) Fig. 4 IR spctr o vrious copolymrs. Ht low (Enothrm up) PHP (T g = o C) PHP (T g = o C) Tmprtur ( o C) Fig. 5 DC curvs o PHP n PHP. 5

6 Elctronic upplmntry Mtril (EI) or Polymr Chmistry This ournl is Th Royl ocity o Chmistry 2014 () (c) () () Fig. 6 Typicl TEM imgs o copolymr miclls orm y CP (, ) n ggrgts involving lrg compoun miclls orm y ACG (c, ) in quous solution (c = 0.50 mg ml 1). 6

7 Elctronic upplmntry Mtril (EI) or Polymr Chmistry This ournl is Th Royl ocity o Chmistry 2014 Conition, D (D pk ), PD () 4 h, 11 (2.2, 209), Intnsity (%) () 24 h, 13 (206), () 12 h, 204 (223), (c) 2 h, 201 (215), () ph 7.4 (15 ), 15 (179), () ph 7.4, 156 (173), Dimtr (nm) Fig. 7 DL plots o ACG ggrgts (c = 0.50 mg ml 1 ) in PB solution (50 mm) t 37 o C: n, ph 7.4; c-, ph 5.0. Conition, D (D pk ), PD () 4 h, 131 (145), Intnsity (%) () 24 h, 129 (140), 0.02 (c) 6 h, 133 (142), () 2 h, 14 (15), () ph 7.4, 156 (173), Dimtr (nm) Fig. DL plots o ACG ggrgts (c = 0.50 mg ml 1 ) in PB solution (ph 7.4, 50 mm) t 37 o C:, no DTT; -, 10 mm DTT. 7

8 Elctronic upplmntry Mtril (EI) or Polymr Chmistry This ournl is Th Royl ocity o Chmistry () 4 M n (kg/mol) ph mm DTT ph mm DTT Tim (h) wt/logm riginl (59600, 1.0) t = 6 h (46900, 1.15) t = 12 h (40200, 1.13) t = 24 h (31000, 1.12) t = 4 h (23900, 1.12) () logmw Fig. 9 Dpnnc o molculr wight o clv ACG copolymr upon xtrnl stimuli in PB solution (50 mm) t 37 o C on tim () n typicl GPC trcs o clv copolymrs otin t irnt tims ().