Supporting Information

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1 Supporting Informtion Ethylbromoisobutyrte (EBIB), tin (II) 2-ethylhexnote (Sn(EH) 2 ), copper (II) bromide (CuBr 2 ), toluene, sodium zide, dimethylformmide (DMF), nd N, N, N, N, N pentmethyltriethylenedimine (PMDETA) were used s received. Tris[2-(dimethylmino) ethyl]mine (Me 6 TREN) ws synthesized following previously reported procedure. 1 TMSS ws polymerized by Activtors Regenerted by Electron Trnsfer Atom Trnsfer Rdicl Polymeriztion (ARGET ATRP). The generl procedure is s follows: TMSS nd toluene were first dried over clcium hydride. Dry TMSS (23.05 g, mmol), EBIB (554mg, 2.8 mmol), CuBr 2 (6.3 mg, mmol), Me 6 TREN (65 mg, mmol), nd dry toluene (27.5 ml) were dded to round bottom flsk. The solution ws degssed with high-purity rgon for 10min nd then Sn(EH) 2 (115 mg, mmol) ws dded vi syringe. The solution ws submerged in n oil bth t 90 C nd polymerized for three hours nd twenty minutes t which point it reched pproximtely 40% conversion. Different moleculr weights were obtined by using the sme rection conditions described bove nd chnging the rection time, thus chnging the conversion. The polymer ws precipitted in methnol nd dried under vcuum. PTMSS (6000 mg, 1.7 mmol), sodium zide (325 mg, 5.0 mmol), nd 80mL DMF were dded to round bottom flsk. The rection ws stirred overnight t room temperture. The polymer ws precipitted in methnol, dried, dissolved in THF, nd reprecipitted in methnol three times to remove excess sodium zide slt. The ethynyl-oligoscchrides nd PTMSSAz polymers were coupled by zidelkyne cycloddition. The generl procedure is s follows: ethynyl-oligoscchride (0.23 g, 0.18 mmol) nd PTMSSAz (0.36 g, 0.14 mmol) were dissolved in 20mL DMF in seprte flsks. PMDETA (0.045 ml) ws dded to the oligoscchride flsk. The flsks were degssed with high-purity rgon for 10 minutes nd then cnnulted to third flsk contining CuBr under rgon tmosphere (40.2 mg, 0.28 mmol). The solution turned green nd ws stirred for 72 h t 40 C. The solution ws pssed through bsic lumin to remove the copper, concentrted under vcuum, nd precipitted in methnol. Tble SI-1. Properties nd compositions of polymers exmined in this study Smple Mn PMTSS Mn Sugr b PDI PTMSS (g/mol) (g/mol) Volume % PTMSS c MH-PTMSS XGO-PTMSS BCyD-PTMSS MH-PTMSS Moleculr weight of bromine-terminted PTMSS determined using dn/dc of b PDI of oligoscchrides re ssumed to be 1.00 c Volume percentges clculted using density of g/cm 3 for PTMSS 3 nd the density of mylose, g/cm 3 for the oligoscchrides

2 Figure SI-1. NMR spectr showing the complete trnsformtion from ) bromine-terminted PTMSS to b) zide-terminted PTMSS. As shown in the mgnified imge, there is no evidence of bromineterminted PTMSS in the zide-terminted PTMSS 1 H NMR, indicting complete end group trnsformtion. In b), pek d is residul THF. b b c d e

3 Figure SI-2. Representtive normlized GPC trces from the refrctive index detector showing pek shifts to higher moleculr weight polymer from the PTMSS 26 precursor (-) to the block copolymers (MHb-PTMSS 26 ( ), XGO-b-PTMSS 26 ( ), nd βcyd-b-ptmss 26 ( x ))

4 Figure SI-3. Representtive normlized trnsmission IR spectr of )PTMSSBr b)ptmssaz c)ptmss-boligoscchride fter coupling. Pek 1 shows the presence of OH groups in the oligoscchride block copolymer, pek 2 indictes the presence of zide in the PTMSS homopolymer, nd peks 3 re representtive of CO 2 contmintion b c 3 2 1

5 Figure SI-4. DSC trces of PTMSS, which shows glss grnsition round 110 C, MH, XGO, nd βcyd, which do not exhibit glss trnsitions or melt trnsitions below the degrdtion tempertures of the mterils Figure SI-5. TGA dt showing the degrdtion of PTMSS, MH, XGO, nd βcyd

6 Figure SI-6. βcyd-b-ptmss 26 ) s-cst nd b) fter solvent nneling b 50 nm Figure SI-7. Dynmic light scttering on 0.5 wt% solutions in toluene of ) MH-PTMSS 26 showing pek prticle rdius of nm, b) XGO-b-PTMSS 26 showing pek prticle rdius of 8.59 nm, c) βcyd-b- PTMSS 26 showing pek prticle rdius of 6.30 nm, nd d) MH-PTMSS 15 showing pek prticle rdius of 8.25 nm 15 Intensity (%)

7 b Intensity (%) c Intensity (%) d 15 Intensity (%)

8 References 1. Fu, G. D.; Xu, L. Q.; Yo, F.; Zhng, K.; Wng, X. F.; Zhu, M. F.; Nie, S. Z., ACS Applied Mterils & Interfces 2009, 1 (2), Hrd, M.; Suzuki, T.; Ohy, M.; Kwguchi, D.; Tkno, A.; Mtsushit, Y.; Toriki, N., Journl of Polymer Science Prt B: Polymer Physics 2005, 43 (12), Hrd, M.; Suzuki, T.; Ohy, M.; Kwguchi, D.; Tkno, A.; Mtsushit, Y., Mcromolecules 2005, 38 (5), Tkhshi, Y.; Kumno, T.; Nishikw, S., Mcromolecules 2004, 37 (18),