Electrostatic Assembly Of Functional. Polymer Combs Onto Gold Nanoparticle. Surfaces: Combining RAFT, Click And LbL

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1 upplmntry Mtril (EI) or Polymr Chmistry This journl is () Th Royl oity o Chmistry 2010 upportin Inormtion Eltrostti Assmly Funtionl Polymr Coms nto Gol noprtil urs: Cominin RAFT, Clik An LL To Gnrt w Hyri nomtrils Antoin Bousqut, Cyrill Boyr*, Thoms P. Dvis, Mrtin H. tnzl * Cntr or Avn Mromolulr Dsin (CAMD), hool o Chmil Eninrin, Univrsity o w outh Wls, yny, Austrli. Fx: ; Tl: ; -mil: m.stnzl@unsw.u.u,.oyr@unsw.u.u tol un X k m l tolun X H h i j H h j +j +n l k 0.5 m n n n Fiur I-1: 1 H MR o th tba opolymristion with HEA us or th trmintion o onvrsion. 1

2 upplmntry Mtril (EI) or Polymr Chmistry This journl is () Th Royl oity o Chmistry 2010 Fiur I-2: PnBA. 1) 1 H MR o PnBA 1. 2) GPC tr (in THF) o PnBA 1. 3) GPC tr o PnBA 2. 2

3 upplmntry Mtril (EI) or Polymr Chmistry This journl is () Th Royl oity o Chmistry ) n ) Fiur I-3: P. 1) 1 H MR o P. 2) GPC tr (in THF) o P. 3

4 upplmntry Mtril (EI) or Polymr Chmistry This journl is () Th Royl oity o Chmistry ) n CDCl 3 X ) Fiur I-4: 1) 1 H MR o PtBA. 2) GPC tr (in THF) o PtBA. 4

5 upplmntry Mtril (EI) or Polymr Chmistry This journl is () Th Royl oity o Chmistry ) ) Fiur I-5: 1) 1 H MR o PEGMEA (ot: inits th CH in jnt position o RAFT n-roup, i.. -(C)-; 2) GPC tr (in DMA) o PEGMEA. 5

6 upplmntry Mtril (EI) or Polymr Chmistry This journl is () Th Royl oity o Chmistry 2010 Tl I-1: Rsults rom th UV titrtion o th in untionlity on th kon. A 0 0 mol/l A 0 - in Fiur I-6. UV lirtion urv o nzyl pyriin-2-ylithioormt in hloroorm solution t λ = 517 nm. A 0, A, 0 n r th sorn n th onntrtion o th P(tBA-r-HEAin) os solution t tim zro n t th n. 6

7 upplmntry Mtril (EI) or Polymr Chmistry This journl is () Th Royl oity o Chmistry ) k h k j h +i ) Fiur I-7: 1 H MR o th PtBA-r-HEAin us or th in titrtion y UV sptrosopy. 7

8 upplmntry Mtril (EI) or Polymr Chmistry This journl is () Th Royl oity o Chmistry 2010 Fiur I-8: uprposition o th GPCs trs (in THF) o PnBA 2 (sh), P(tBA-r- HEAin) (ot) n PtBA--PnBA2 X=1 (ull lin). 8

9 upplmntry Mtril (EI) or Polymr Chmistry This journl is () Th Royl oity o Chmistry FiurI-9: 1 H MR ptrum o PtBA--PnBA2 (X=1). 9

10 upplmntry Mtril (EI) or Polymr Chmistry This journl is () Th Royl oity o Chmistry 2010 h h Fiur I-10: 1 H MR ptrum o PtBA--PnBA2 (X=1.5). Fiur I-11: uprposition o th GPCs trs (in THF) o PtBA--PtBA X=1 (ull lin) n PtBA--PtBA X=1.5 (sh). 10

11 upplmntry Mtril (EI) or Polymr Chmistry This journl is () Th Royl oity o Chmistry Fiur I H MR sptrum o PtBA--PtBA X=1.5. Fiur I-13. GP: uprposition o th GPCs trs (in THF) o PtBA--P X=1 (ull lin) n PtBA--P X=1.5 (sh). 11

12 upplmntry Mtril (EI) or Polymr Chmistry This journl is () Th Royl oity o Chmistry Fiur I-14: 1 H MR sptrum o PtBA--P X=

13 upplmntry Mtril (EI) or Polymr Chmistry This journl is () Th Royl oity o Chmistry 2010 Fiur I-15: uprposition o th GPCs trs (in THF) o PtBA--PEGMEA X=1 (ull lin) n PtBA--PEGMEA X=1.5 (sh). 13

14 upplmntry Mtril (EI) or Polymr Chmistry This journl is () Th Royl oity o Chmistry 2010 i i h, Fiur I-16: 1 H MR sptrum o PtBA--PEGMEA X=

15 upplmntry Mtril (EI) or Polymr Chmistry This journl is () Th Royl oity o Chmistry 2010 Fiur I-17: 1 H MR sptrum o PAA--PAA. 15

16 upplmntry Mtril (EI) or Polymr Chmistry This journl is () Th Royl oity o Chmistry 2010 H Fiur I-18: 1 H MR sptrum o PAA--P. 16

17 upplmntry Mtril (EI) or Polymr Chmistry This journl is () Th Royl oity o Chmistry 2010 x y z H i Fiur I-19: 1 H MR sptrum o PAA--PEGMEA X=

18 upplmntry Mtril (EI) or Polymr Chmistry This journl is () Th Royl oity o Chmistry 2010 A umr istriution iz (nm) B Fiur I-20: A- Dynmi liht sttrin o nk ol nnoprtils, inst: typil pitur o th GPs solution; B- TEM piturs o nk GPs. 18

19 upplmntry Mtril (EI) or Polymr Chmistry This journl is () Th Royl oity o Chmistry 2010 Rltiv Intnsity (KCPs) A B C Binin Enry (V) / tomi rtio /C tomi rtio GPs/PEI GPs/PEI/PAA GPs/PEI/PAA--PEGMEA Fiur I-21: XP sptr o GPs moii polymrs orm y th LBL pross; (1s) sptr o A- GPs/PEI; B- GPs/PEI//PAA; C- GPs/PEI/PAA--PEGMEA; B- / n /C tomi rtios or GPs/PEI, GPs/PEI/PAA n GPs/PEI/PAA--PEGMEA. 19

20 upplmntry Mtril (EI) or Polymr Chmistry This journl is () Th Royl oity o Chmistry 2010 Croxyli i on (1720 m -1 ) Estr Bon (1730 m -1 ) Asorn Wvlnth (m -1 ) Estr on (1726 m -1 ) Wvlnth (m -1 ) Fiur I-22: ATR-IRTF sptr o (top) purii PtBA--P X=1.5 n (ottom) purii o PtBA--PtBA X=

21 upplmntry Mtril (EI) or Polymr Chmistry This journl is () Th Royl oity o Chmistry 2010 A t nutrl ph (6.5) i ph (3.0) Rltiv Intnsity t n utrl ph i ph (3.0 ) iz (nm) B 1.0 t nutrl ph (6.5) t lo w ph (3.0 ) 0.5 Asorn t nutrl ph (6.5) t low ph (3.0) Wvlnth (nm) Fiur I-23: A- Dynmi liht sttrin o (top) GPs/PEI/PAA--PEGMEA n (ottom) GPs/PEI//PAA; B- UV-visil o (top) GPs/PEI//PAA n (ottom) GPs/PEI/PAA--PEGMEA t irnt ph. 21