nitrobenzyl chloride (99%, Aldrich), hexamethyldisilazane (HMDS, 99%, Aldrich),

Size: px

Start display at page:

Download "nitrobenzyl chloride (99%, Aldrich), hexamethyldisilazane (HMDS, 99%, Aldrich),"

Aubrie Terry
6 years ago
Views:

1 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, Minz, Grmny Tl: ; Fx: ; 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 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.

2 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 ), (m, 2, C 2 ), (t, 2, C 2 ), (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, ), (s, 1, ). 2 2 C 170 o C DMS Cl K2C3, DMF 2 Si(Et) 3 2PtCl 6 2 Si(Et) 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 ), (m, 2, C 2 ), (m, 1, C=C 2 ), 5.79 (s, 1, romti rin), (m, 1, C=C 2 ), 7.70 (s, 1, ). 13 C MR (63 Mz, DMS- 6, δ ppm ): 23.24, 41.40,

3 Eltroni Supplmntry Mtril (ESI) or Chmil Communitions This ournl is Th Royl Soity o Chmistry , 99.38, , , , , , , , , , , , (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 yllow soli ws otin (yil 80%). 1 MR (250 Mz, DMS- 6, δ ppm ): 2.31 (s, 3, ArC 3 ), (m, 2, C 2 ), (m, 2, C=C 2 ), 5.72 (s, 2, ArC 2 ), (, 1, C=C 2 ), 6.46 (s, 1, Ar), (m, 1, Ar), (m, 2, Ar), (, 1, Ar), (t, 1, ), 9.61 (s, 1, ). 13 C MR (63 Mz, DMS- 6, δ ppm ): 23.04, 41.24, , , , , , , (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 ): (t, 2, SiC 2 ), (m, 9, C 3 ), (m, 2, SiC 2 C 2 ), 2.31 (s, 3, ArC 3 ), (m, 2, C 2 ), (m, 6,

4 Eltroni Supplmntry Mtril (ESI) or Chmil Communitions This ournl is Th Royl Soity o Chmistry 2012 C 2 ), 5.68 (s, 2, ArC 2 ), (s, 1, Ar), 6.97 (s, 1, ), (m, 1, Ar), 7.57 (m, 2, Ar), (, 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.

5 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

6 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

7 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 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

9 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

10 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,

Glucose Sensitivity of Boronic Acid Block Copolymers at Physiological ph

Glucose Sensitivity of Boronic Acid Block Copolymers at Physiological ph Eltroni Supporting Informtion for Gluos Snsitivity of Boroni Ai Blok Copolymrs t Physiologil p Dshish Roy n Brnt S. Sumrlin* * Dprtmnt of Chmistry n th Cntr for Drug Disovry, Dsign, n Dlivry Southrn Mthoist