Synthesis of Dextran Graft Copolymers The synthesis route of the dextran graft copolymers is shown in Scheme S1. The details for

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1 Supportin information Synthesis of Dextran Graft Copolymers The synthesis route of the dextran raft opolymers is shown in Sheme S1. The details for the synthesis of raft opolymers are as follows. Sheme S1. The synthesis route of Dex--PMAGGCNTyr-NPEG 3k (II), Dex--P(MPEG-o-MAGGCNTyr) (III), Dex--P(PMA-o-MAGGCNTyr) (IV). Synthesis of Dex--P(MPEG-o-MAGGCNTyr) and Dex--P(PMA-o- MAGGCNTyr). Dextran (250 m) was firstly dissolved in 6 ml water and then K 2 S 2 8 (2.7 m, 0.01 mmol), NaS 3 (1.4 m, 0.01 mmol) were added. The solution was uled with nitroen at room temperature for 30 min to remove the oxyen. Then 4 ml MAGGC/MPEG or MAGGC/PMA mixed aqueous solution was added slowly 1

2 under nitroen atmosphere. The resultant reation solutions were dialyzed aainst water, and then were freeze-dried to otain Dex--P(MPEG-o-MAGGC) or Dex--P(PMA-o- MAGGC). The details on the seletion of the optimal onditions are listed in Tales S1 and S2. From run 1 to 4 (Tale S1), when n(-c):n(mpeg) is kept at 1.95:1, DS -C /DS MPEG 1, so the raft monomer MAGGC/MPEG reativity ratio is around 1:2, From run 1 to 3 (Tale S2), when n(-c):n(pma) is kept at 0.77:1, DS -C /DS MPEG 0.8, so the raft monomer reativity ratio MAGGC/PMA is around 1:1. In order to synthesize raft opolymer with a deree of sustitution of C roups around , the reation feedin ratios of the MAGGC were adjusted as those listed in Tales S1 and S2. DS PMA and DS MPEG inrease with the inrease of the mass of the added monomer PMA or MPEG. The influenes of MPEG and PMA mononmer onentrations on the raft ratio (G) are listed in Tales S1 and S2. Graftin ratio (G) was alulated y the followin formula. G = W 2 /W 1 100%, where W 1 and W 2 the mass of pure raft opolymer and raft hains, respetively. DS PMA = A 2 /2A 1, where A 1 and A 2 are the interated areas of the protons on dextran akone (δ = 4.95 ppm) and the methylene of =C N C 2 roups of the PPMA side hains (δ = ppm) on 1 NMR spetra, respetively. DS MPEG = A 3 /2A 1, where A 3 is the methylene of =C C 2 roups of the PMPEG side hains (δ = ppm) on 1 NMR spetra, respetively. Moleular weiht of Dex--P(MPEG-o- MAGGC) raft opolymer was alulated y M w,dex--p(mpeg-o-maggc) = M w,dex + n(184 DS C DS MPEG ), where M w,dex is the moleular weiht of dextran, 184 is the molar mass of MAGGC. Moleular weiht of Dex--P(PMA-o-MAGGC) raft opolymer was alulated y M w,dex--p(pma-o-maggc) = M w,dex + n(184 DS C DS PMA ), where 143 is the molar mass of PMA. n is the averae numers of luose unit per dextran hain. The raft opolymers are haraterized y usin 1 NMR, and the 2

3 typial 1 NMR data is shown in Fiure S1 and S2. The onjuation of the L-Tyrosine is similar to the previous work. 1 Dex--P(MPEG-o-MAGGCNTyr). Yield 74%. 1 NMR (400 Mz, D 2, δ, ppm): (3, m, -C 3 ), (2, m, -C-C 2 -), 2.70 (2, s, -C 2 - from L-Tyrosine), (2, m, =C--C 2 - from PMPEG), (9, m, dextran), 4.95 (1, s, 1 from rin of dextran), 6.70 (2, s, m-phenyl hydroen), 7.10 (2, s, o-phenyl hydroen). Dex--P(PMA-o-PMAGGCNTyr). Yield 79.6%. 1 NMR (400 Mz, D 2, δ, ppm): (3, m, -C 3 ), (2, m, -C-C 2 -), 2.70 (2, s, -C 2 - from L-Tyrosine), (2, m, -C 2 - from PMA), (9, m, dextran), 4.95 (1, s, 1 from rin of dextran), 6.70 (2, s, m-phenyl hydroen), 7.10 (2, s, o-phenyl hydroen). Tale S1. Details of synthesis and information for Dex--P(MPEG-o-MAGGC). a m Dex :m [-C] n [-C] : DS -C / G MAGGC G MPE M w Run m Dex DS -C DS MPEG :m [MPEG] n [MPEG] DS MPEG % G% (kda) :0.25:0.25 2: :0.5:0.5 2: :1:1 2: :1.5:1.5 2: :1.5: a [K 2 S 2 8 ] = [NaS 3 ] =1 mmol/l. All the reations were arried out at 30 C for 9 h. The deree of sustitution of the MAGGC (DS MAGGC ) and MPEG (DS MPEG ) per luose unit were alulated y 1 NMR. M w is the moleular weiht of Dex--P(MPEG-o-MAGGC), and is alulated y 1 NMR. Tale S2. Details of synthesis and information for for Dex--P(PMA-o-MAGGC). a Run m Dex (m) m [Dex] :m [-C] :m [PMA] n [-C] : n [MPEG] DS -C DS PMA DS -C / DS PMA G -C % G PMA % M w (kda) :0.25: : :0.5: : :1:1 0.8: :1: a [K 2 S 2 8 ] = [NaS 3 ] =1 mmol/l. All the reations were arried out at 30 C for 9 h. The deree of sustitution of the MAGGC (DS MAGGC ) and PMA (DS PMA ) per luose unit were alulated y 1 NMR. M w is the moleular weiht of Dex--P(PMA-o-MAGGC), and is alulated y 1 NMR. 3

4 6 6 Eletroni Supplementary Material (ESI) for Polymer Chemistry Dex N N N N C e f N d e f d Dex N N * C 2 a n a Chemial shift (ppm) Fiure S1. 1 NMR spetra of Dextran, Dex--P(MPEG-o-MAGGC) and Dex--P(MPEG-o-MAGGCNTyr) at 400 Mz in D 2. y Dex x-y m N N N e f C N 3 N N C d ef d Dex x-y m N N C 3 N * C 2 a n a ppm Chemial shift Fiure S2. 1 NMR spetra of Dextran, Dex--P(PMA-o-MAGGC) and Dex--P(PMA-o-MAGGCNTyr) at 400 Mz in D 2. 4

5 Synthesis of Dex--PMAGGCNPEG 3k -NTyr Copolymers. Dex--PMAGGC (DS -C = 0.57) (50 m) was dissolved in water to otain a solution with p of Then ertain amounts of EDC/NS were added and stirred for 10 min for pre-ativation, after whih L-Tyrosine, N 2 PEG 3k and Na 2 C 3 mixed solution was added dropwise. The reation mixture was kept in water ath at 25 C and stirred for 3 h. Dex--PMAGGCNPEG 3k -NTyr was otained y the previous purified method. The optimism of the reation onditions are listed in Tale S3. Dex--PMAGGC with 0.57 of DS C was hosen for amide reation aordin to our previous work, DS NPEG3k is determined y the mass of the added N 2 PEG 3k. The ontent of N 2 PEG 3k in the side hain PMAGGC of raft opolymers, whih was defined as the averae N 2 PEG 3k roups per luopyranose unit (DS NPEG3k ), an e estimated y DS NPEG3k = (A 4 -A 5 )/280, where A 4 : the interated areas from δ 3.45 to 4.12 ppm of raft opolymer Dex--PMAGGCNPEG 3k -NTyr, A 5 : the interated areas from δ 3.45 to 4.12 ppm of raft opolymer Dex--PMAGGC, 280: all the numers of hydroen atom per PEG hain. Moleular weiht of Dex--PMAGGCNPEG 3k -NTyr raft opolymers were alulated y M w, Dex--PMAGGCNPEG3k = M w,dex + n(184 ( DS NPEG3k ) DS NPEG3k ) where M w,dex is the moleular weiht of dextran, n is the averae numers of luose unit per dextran hain. 184 is the molar mass of MAGGC, 0.57 is the DS C of the Dex--PMAGGC raft opolymers that used for the amide formation Dex--PMAGGCNPEG 3k -NTyr. Yield 71%. 1 NMR (400 Mz, D 2, δ, ppm): (3, m, -C 3 ), (2, m, -C-C 2 -), 2.70 (2, s, -C 2 - from L-Tyrosine), (m, dextran and -C 2 -C 2 - from N 2 PEG 3k ), 4.95 (1, s, 1 from rin of dextran), 6.70 (2, s, m-phenyl hydroen), 7.10 (2, s, o-phenyl hydroen). 5

6 Tale S3. Details of synthesis and information for Dex--PMAGGCNPEG 3k -NTyr. a Run m Dex--PMAGGC (m) m PEG (m) m Tyr (m) n [C] :n [PEG] :n [ Tyr]:n [EDC] :n [NS] DS PEG3k N Tyr M w (kda) :0.025:1:1: :0.05:0:1: :0.1:1:1: :0.2:0:1: :0.3:0:1: a Reation at p = 10-11, adjusted y Na 2 C 3, pre-ativited for 10 min, All the reations were arried out at 25 C for 3 h. The averae numers of MAGGC per luose rin is M w is the moleular weiht of Dex--PMAGGCNPEG 3k -NTyr, and is alulated y 1 NMR. Fiure S3. Representative ITLC hromatorams of 125 I laeled Dex--PMAGGCNPEG 3k -NTyr. (a) the oriinal kit and () after purifiation. 6

7 Fiure S4. Representative ITLC hromatorams of 125 I laeled Dex--P(MPEG-o-MAGGCNTyr). (a) the oriinal kit and () after purifiation. Referene 1. D. Wan, J. Shi, J. Tan, X. Jin, Q. Li,. Kan, R. Liu, B. Jia and Y. uan, Biomaromoleules, 2011, 12,