Eltroni Supplmntry Mtril (ESI) or Chmil Communitions This ournl is Th Royl Soity o Chmistry 2012 Supportin inormtion Sl-hlin hyrol s on multivlnt -onin Jixi Cui, Aránzzu l Cmpo* Mx-Plnk-Institut ür Polymrorshun, Akrmnnw 10, 55128 Minz, Grmny Tl: +49 6131 379563; Fx: +49 6131 379271; E-mil: lmpo@mpipminz.mp. Exprimntl Mtrils n mthos. 2-Isoyntothyl mthrylt (98%, Alrih), llyl isoynt (98%, Alrih), 2- nitronzyl hlori (99%, Alrih), hxmthylisilzn (MDS, 99%, Alrih), trithoxysiln (99%, Alrih), 2 PtCl 6.x 2 (38% Pt sis, Sim), n 6-mthylisoytosin (MIS, 99%, Aros) wr us s riv. 2-(Dimthylmino)thyl mthrylt (DMAEMA, 98%, Alrih), 2-hyroxythyl mthrylt (EMA, 97%, Alrih), 2-(2-mthoxythoxy)thyl mthrylt (ME2MA, 95%, Alrih), -isopropylrylmi (IPAm, 98%, Alrih),, - imthylrylmi (DMAA, 99%, Alrih), n,'-mthyln isrylmi (MBA, 99%, Alrih) wr pss throuh sili olumn to rmov inhiitor or us. All othr rnts n solvnts wr us s otin unlss othrwis spii. Solution 1 n 13 C sptr wr msur in CDCl 3 or DMS- 6 solution t 25 ºC on Brukr Ultr Shil 250 Mz sptromtr. UV sptr wr ror on Vrin Cry 4000 UV-vis sptromtr (Vrin In. Plo Alto, CA). Mss sptr wr ror on Miromss Finnin- MAT ZAB-S mss sptromtr. Gl prmtion hromtorphy (GPC) ws prorm with polymr stnr srvi (PSS) quipp with WinGPC. RI ERC 7512(ERMA In.) n UV Visil S-3702(SMA) wr us s ttors. Ttrhyroorn (TF) ws mploy s lunt t low rt o 1.0 ml/min t 60 ºC n olumns SDV rom PSS (100, 103, 104, n 106 A porosity; 10 mm siz; imnsions o 0.8-30 m). GPC urvs wr lirt inst polystyrn stnrs. Mirosopy piturs wr ror on Ziss Axioskop polrizin liht mirosop quipp with Linkm TMS 91/TMS 600 htin st.
Eltroni Supplmntry Mtril (ESI) or Chmil Communitions This ournl is Th Royl Soity o Chmistry 2012 Synthsis 2 C 170 o C DMS SCMMA Shm S1: Synthsis o SCMBMA monomr 2-(3-(6-Mthyl-4-oxo-1,4-ihyropyrimiin-2-yl)urio)thyl mthrylt (SCMBMA). 1 6-Mthylisoytosin (MIS, 2.0, 16.0 mmol) ws to 50mL o DMS n ht up to 170 C or 10 min. n th soli issolv, th oil th ws rmov. 2-Isoyntothyl mthrylt (2.75, 17.7 mmol) ws immitly to th lsk unr viorous stirrin. Th mixtur ws quikly ool usin wtr th. A in whit soli pripitt upon oolin. Th pripitt ws ollt n wsh with xss ton n ri unr vuum to otin 4.03 o whit soli (yil 90%). 1 MR (250 Mz, DMS-6, δ ppm ): 1.89 (s, 3, C 3 ), 2.11 (s, 3, ArC 3 ), 3.43-3.50 (m, 2, C 2 ), 4.15-4.20 (t, 2, C 2 ), 5.70-5.72 (m, 1, C=C 2 ), 5.79 (s, 1, romti rin), 6.07(s, 1, C=C 2 ), 7.60 (s, 1, ), 9.79 (s, 1, ), 11.43 (s, 1, ). 2 2 C 170 o C DMS Cl K2C3, DMF 2 Si(Et) 3 2PtCl 6 2 Si(Et) 3 2 3 1 Shm S2: Synthsis o th UPy-s siln ouplin nt 1-(3-(6-Mthyl-4-oxo-1,4-ihyropyrimiin-2-yl)urio)prop-2-n (2) 6-Mthylisoytosin (MIS, 1.0, 8.0 mmol) ws to 25mL o DMS n ht up to 170 C or 10 min. n th soli issolv, th oil th ws rmov. Allyl isoynt (0.66, 8.0 mmol) ws immitly to th lsk unr viorous stirrin. Th mixtur ws quikly ool usin wtr th. A in whit nl rystl pripitt upon oolin. Th pripitt ws ollt n wsh with xss ton n ri unr vuum to otin 1.60 o whit soli (yil 96%). 1 MR (250 Mz, DMS- 6, δ ppm ): 2.11 (s, 3, ArC 3 ), 3.77-3.82 (m, 2, C 2 ), 5.09-5.22 (m, 1, C=C 2 ), 5.79 (s, 1, romti rin), 5.80-5.93(m, 1, C=C 2 ), 7.70 (s, 1, ). 13 C MR (63 Mz, DMS- 6, δ ppm ): 23.24, 41.40,
Eltroni Supplmntry Mtril (ESI) or Chmil Communitions This ournl is Th Royl Soity o Chmistry 2012 64.24, 99.38, 114.48, 124.87, 129.25, 129.52, 131.76, 134.11, 135.49, 147.31, 153.71, 157.51, 167.95, 169.00 (16C). EIMS m/z: 209 [M] +. Mlt point: 248 o C (rystl rom DMS) 1-(3-(4-Mthyl-6-((2-nitronzyl)oxy)pyrimiin-2-yl)urio)prop-2-n (3) To mixtur o 2 (1.0, 5 mmol) n K 2 C 3 (1.38, 10 mmol) in 25 ml o ry DMF, 2-nitronzyl hlori (1.03, 6 mmol) ws. Th mixtur ws stirr t 90 o C or 12 h. Th solution ws pour into 200 ml wtr n thn xtrt with thyl tt. Th orni lyr ws ri ovr with nhyrous MS 4. Atrwrs th solvnt ws rmov unr ru prssur n th rsiu ws purii y olumn hromtorphy on sili l usin ihloromthn/thyl tt (10/1, v/v) s lunt. 1.38 yllow soli ws otin (yil 80%). 1 MR (250 Mz, DMS- 6, δ ppm ): 2.31 (s, 3, ArC 3 ), 3.81-3.85 (m, 2, C 2 ), 5.04-5.19 (m, 2, C=C 2 ), 5.72 (s, 2, ArC 2 ), 5.84-5.95 (, 1, C=C 2 ), 6.46 (s, 1, Ar), 7.61-7.65 (m, 1, Ar), 7.74-7.78 (m, 2, Ar), 8.12-8.15 (, 1, Ar), 9.18-9.22 (t, 1, ), 9.61 (s, 1, ). 13 C MR (63 Mz, DMS- 6, δ ppm ): 23.04, 41.24, 104.50, 115.17, 134.96, 151.25, 157.78, 161.39, 164.62 (9C). EIMS m/z: 344 [M ] +. Mlt point: 128 o C. 3-(3-(4-Mthyl-6-((2-nitronzyl)oxy)pyrimiin-2-yl)urio)propyltrithoxylsiln (1) In prviously MDS-pssivt ry, roun-ottom lsk, 3 (0.5, 1.46 mmol) n trithoxysiln (3.6, 21.6 mmol) wr ht to 80 o C unr n ron tmosphr. 2 PtCl 6 isopropnoli solution (100 μl, 0.03 m/μl) ws n th mixtur ws stirr or 4 h t 80 o C. Atr th rtion, xss trithoxysiln ws rmov in vuum, n th soli rsiu ws tkn up in ihloromthn n iltr throuh Clit500. Th iltrt ws onntrt unr ru prssur n trmin to 1 in 45% mixtur with th ru ompoun. 1 MR (250 Mz, CDCl 3, δ ppm ): 0.59-0.65 (t, 2, SiC 2 ), 1.12-1.21 (m, 9, C 3 ), 1.59-1.62 (m, 2, SiC 2 C 2 ), 2.31 (s, 3, ArC 3 ), 3.20-3.31 (m, 2, C 2 ), 3.64-3.84 (m, 6,
Eltroni Supplmntry Mtril (ESI) or Chmil Communitions This ournl is Th Royl Soity o Chmistry 2012 C 2 ), 5.68 (s, 2, ArC 2 ), 6. 21 (s, 1, Ar), 6.97 (s, 1, ), 7.42-7.47 (m, 1, Ar), 7.57 (m, 2, Ar), 8.03-8.06 (, 1, Ar), 9.12 (s, 1, ). EIMS m/z: 508 [M ] + Copolymriztion DMAEMA (467 m, 2.97 mmol) n SCMBMA (72 m, 0.26 mmol) wr issolv in 2 ml 1,4-ioxn. Atr pur with ontinuous 2 or 10 min, AIB (5 m) ws n thn th mixtur ws stirr t 70 o C or 10h. Th solution ws ilut with 15 ml 1,4-ioxn, ollowin y pripittin in 400 ml hxn/hloroorm (9/1, v/v). Th pripitt ws ollt y iltr n thn ri unr vuum t 40 o C or 6 h. 485 m whit soli wr otin. Yil 90%. Spiy hrtriztion, lultion o opolymr omposition, init MR sptr low. Qurtz rystl miroln with issiption monitorin (QCM-D) Th sustrts (QCM-D rystl ot y silion) wr ln y plsm oxition or 10 min usin s mixtur o oxyn n ron (1:9) n thn immrs in siloxn rivtiv TF solution (1wt%) ontinin 0.01% 1 M quous solution or 2h. Atr wsh with TF n wtr, th silion sustrts wr k t 90 o C or 1 h. Irrition xprimnts wr rri out usin LED-UV liht o 365 nm (PolyhromV lmp (TILL Photonis Gm, Grlin, Grmny), 4.7 μw m -2, irrition tim: 1.5h). QCM-D msurmnts (rquny hn n issiption tor D) wr rri out in Q-Sns E1 systm (Swn). A sili-ot rystl ws us (Q-Sns, Swn). Th rystl ws xit t its unmntl rquny (5 Mz), n msurmnts wr prorm t th irst, thir, ith, svnth, ninth, n thirtn ovrtons, orrsponin to 5, 15, 25, 35, 45, n 55 Mz. Chloroorm or 10 mm Tris Cl quous solution (p 8) without/with opolymr t onntrtions o 2 m/ml wr us s low miums. Prprtion o ovlnt rosslink hyrol To mixtur o SCMBMA (180 m), DMAEMA (1 ), n MBA (20 m) in 4 ml 2 M Cl quous1 solution, 0.2 ml 2 S 2 8 solution (40 m/ml) ws n thn th mixtur ws ht up to 70 o C in sl tu or 20h, lin to hyrol. Rsultin hyrol ws immrs in sturt C 3 quous solution (100 ml) or 48 h or urthr msurmnt.
Eltroni Supplmntry Mtril (ESI) or Chmil Communitions This ournl is Th Royl Soity o Chmistry 2012 An quivlnt strty ws us or EMA, IPAm, ME2MA, n DAMM
Eltroni Supplmntry Mtril (ESI) or Chmil Communitions This ournl is Th Royl Soity o Chmistry 2012 Fiur S1. 1 MR sptr o SCMBMA in DMS- 6 or CDCl 3 In DMS- 6 In CDCl 3 h 3 h 1 h 2 h 3 h 1 h 2 6
Eltroni Supplmntry Mtril (ESI) or Chmil Communitions This ournl is Th Royl Soity o Chmistry 2012 Fiur S2. 1 MR sptrum o opolymr in CDCl 3. Th ompositions wr lult y proton-intrls o (1), n (19.2) 7
8 Fiur S2. 1 n 13 C MR sptr o 2 in DMS- 6 i k k i Eltroni Supplmntry Mtril (ESI) or Chmil Communitions This ournl is Th Royl Soity o Chmistry 2012
Eltroni Supplmntry Mtril (ESI) or Chmil Communitions This ournl is Th Royl Soity o Chmistry 2012 Fiur S3. 1 n 13 C MR sptr o 3 in DMS- 6 h 2 h 1 h 2 h 1 m 1 2 n 3 r o p q o r p q m n 3 1 2 9
Eltroni Supplmntry Mtril (ESI) or Chmil Communitions This ournl is Th Royl Soity o Chmistry 2012 Fiur S3. 1 MR sptrum o 1 in CDCl 3 m n 1 h h n m 2 h h 2 1 (1) K. Ymuhi, J. R. Lizott n T. E. Lon, Mromoluls 2003, 36, 1083-1088 10