Electronic Supplementary Information. Thermally Stable and Photoreactive Polylactides by the Terminal Conjugation of Bio-based Caffeic Acid

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1 Supplmntry Mtril (ESI) for hmil ommunitions This journl is () Th Royl Soity of hmistry 2008 Eltroni Supplmntry Informtion Thrmlly Stbl n Photortiv Polyltis by th Trminl onjugtion of Bio-bs ffi Ai Trn Hng Thi, b Mihiy Mtsuski, n Mitsuru Akshi * Dprtmnt of Appli hmistry, Grut Shool of Enginring, sk Univrsity, 2-1 Ym-ok, Suit , Jpn. kshi@hm.ng.osk-u..jp b Fulty of Thnology of rgni hmistry, ollg of hmistry, Ministry of Inustry, Tin Kin, Lm Tho, Phu Tho, Vit Nm 1. Mtrils 2. Synthsis of polyl-ltis (PLLAs) 2-1. Synthti mtho 2-2. Anlysis of hmil strutur 3. Synthsis of 3,4-itoxyinnmi i (DAA) 4. Synthsis of 3,4-itoxyinnmoyl hlori (DA) 5. Synthsis of DAA-PLLAs 5-1. Anlysis of hmil strutur 5-2. Solubility of PLLAs n DAA-PLLAs 5-3. Thrml proprtis of PLLAs n DAA-PLLAs Anlysis of DS Anlysis of TGA 5-4. rystllinity of PLLAs n DAA-PLLAs 5-5. Photortivity of PLLAs n DAA-PLLAs 5-6. Molulr wight hng of PLLAs n DAA-PLLAs by UV irrition Photo-onjugtion of fluorsnt y onto PLLAs n DAA-PLLA films Synthsis of DHA onjugt Alx fluor Photo-onjugtion mtho of th fluorsnt y onto th films 1

2 Supplmntry Mtril (ESI) for hmil ommunitions This journl is () Th Royl Soity of hmistry Mtrils L-lti (LLA; Tokyo hmil Inustry (TI)) ws rrystlliz from thyl tt, n thn ri in vuo t room tmprtur for 24 h. L-lti i (Tokyo hmil Inustry (TI)) ws us s riv. Thionyl hlori (Sl 2 ), 3,4-ihyroxyinnmi i (DHA), ti nhyri (A 2 ) n Alx fluor 555 vrin isoium slt (Wko Pur hmil Inustris, Lt.) wr us without purifition. 2. Synthsis of polyl-ltis (PLLAs) 2-1. Synthti mtho H H 3 H + H 3 H 3 Snt o -4h H H 3 n H LLA L-lti PLLA n = 14, 36, 50, 73, 112 Shm S1. Th synthsis of PLLA pro vi ring-opning polymriztion (RP) of L-lti using L-lti i s n inititor n tin (II) thyl hxnot (Snt 2 ) s tlyst. PLLA with L-lti/L-lti i t molr rtio of 10/1 mol/mol ws prpr s follows. A totl of 14.4 g of L-lti (100 mmol), 0.9 g of L-lti i (10 mmol) n 43 mg of Snt 2 (0.3 wt% of monomr) ws issolv in 0.43 ml of tolun, n ws mix n mhnilly stirr in vuo t room tmprtur for 1h to rmov ny ir. Tbl S1 Synthti onitions n thrml proprtis of PLLAs Smpl b L-lti L-Lti i M n M w /M n LLA unit Yil T m T (mmol) (mmol) (Mn/72) (wt%) ( o ) ( o ) ( o ) PLLA PLLA PLLA N 333 PLLA N 248 PLLA N 254 Th polymriztion of PLLAs ws rri out in th prsn of Snt 2 s tlyst (0.3 wt% of monomr) with mhnil stirring t 160 o for 4 h. b Th numbrs in th smpl nm r th unit numbrs of LLA. Th molulr wights n numbr of LLA units wr stimt by GP with polystyrn stnrs (lunt: THF). Th yils rprsnt rsults ftr purifition. Th T m n T wr msur by DS upon son hting (10 o min -1 ), th "T " mns th rystlliztion tmprtur. f Th 10% wight-loss tmprturs, T 10, wr msur by TGA unr nitrogn (20 o min -1 ). "N" mns not tt. T 10 f 2

3 Supplmntry Mtril (ESI) for hmil ommunitions This journl is () Th Royl Soity of hmistry 2008 Nxt, th mixtur ws rt t 160 o for 4 h in nitrogn tmosphr. Aftr th rtion, th prout ws issolv in hloroform n purifi by r-pripittion ovr mthnol twi. Th yil ws 78 wt%. Th othr PLLAs wr prpr by n nlogous prour (Tbl S1). Th vrg molulr wight of th PLLAs ws trmin by gl-prmtion hromtogrph (GP) (HL8220GP systm with α M n A900P olumns) in ttrhyrofurn (THF), n thn librt with polystyrn stnrs t flow rt of 0.6 ml/min Anlysis of hmil strutur Th hmil strutur of th PLLA ws nlyz by FT-IR (Figur S1) n 1 H-NMR (Figur S2) msurmnts. () ν - (b) ν Wvnumbr (m -1 ) Figur S1. Rprsnttiv FT-IR sptr of () PLLA50 n (b) L-lti. Th FT-IR sptr of th smpls wr msur t 25 o on Prkin Elmr Sptrum n sptropolrimtr btwn m -1. Th strthing vibrtion pks of th - groups in L-lti wr obsrv t 1267 n 1241 m -1, but wr qunh in th FT-IR sptr of PLLAs n shift to 1211 n 1182 m -1, thus initing tht th PLLAs wr sussfully polymriz. 3

4 Supplmntry Mtril (ESI) for hmil ommunitions This journl is () Th Royl Soity of hmistry 2008 b Dl 3 b () (b) Dl 3 ppm Figur S2. Rprsnttiv 1 H-NMR sptr of () PLLA50 n (b) L-lti. Th 1 H-NMR sptr wr msur with NMR sptromtr (JEL FX 400) t 400 MHz. Th 1 H-NMR hmil shifts in prts pr million (ppm) wr ror ownfil from 7.26 ppm using Dl 3 solvnt s n intrnl rfrn. Th protons of th mthyl or -H groups wr shift into iffrnt position btwn L-lti n PLLAs, n th pks in th sptr of PLLAs wr bror thn in th sptrum of L-lti, thus initing tht th PLLAs wr polymriz. 3. Synthsis of 3,4-itoxyinnmi i (DAA) H H + H 3 H 3 5 H 5 N 0 0-2h, 130 o -5h H 3 H H DHA A 2 DAA H 3 Shm S2. Atyltion of DHA. A totl of 25 g of DHA (140 mmol) ws issolv in 50 ml of istill pyriin t 0 o for 30 min. Nxt, 75 ml of ti nhyri ws n stirr t this tmprtur for 1.5 h. Th mixtur ws thn rt t 130 o unr rflux for 5 h. Aftr th rtion, th prout ws rrystlliz in tolun, wsh by 0.1N Hl twi, n ri t 50 o in vuo for 24 h. Th yil ws 83 wt%. Th hmil strutur of DAA ws stimt by 1 H-NMR msurmnt (Figur S3). 4

5 Supplmntry Mtril (ESI) for hmil ommunitions This journl is () Th Royl Soity of hmistry Dl 3 b f b f ppm Figur S3. 1 H-NMR sptrum of DAA. Th 1 H-NMR sptrum ws msur with NMR sptromtr (JEL FX 400) t 400 MHz. Th 1 H-NMR hmil shifts in prts pr million (ppm) wr ror ownfil from 7.26 ppm using Dl 3 solvnt s n intrnl rfrn. Th 1 H-NMR signls show th prsn of mthyl groups (2.3 ppm) in th DAA, n th intgrl vlu init tht ll H groups of DHA wr strifi with ti nhyri. 4. Synthsis of 3,4-itoxyinnmoyl hlori (DA) H 3 H + Sl 2 DMF 60 o, 7h H 3 l H 3 H 3 DAA DA Shm S3. Synthsis of DA. DA ws synthsiz by 26.4 g of DAA (100 mmol) plus 50 ml of thionyl hlori (Sl 2 ) (700 mmol) using 79 mg of DMF s tlyst in 60 ml of istill ihloromthn s solvnt t 60 o unr rflux for 8 h. Aftr this rtion, th rsiul Sl 2 n solvnt wr rmov in vuo. Th hmil strutur of DA ws nlyz by FT-IR msurmnt (Figur S4). 5

6 Supplmntry Mtril (ESI) for hmil ommunitions This journl is () Th Royl Soity of hmistry 2008 () (b) ν = (toxyl n rbonyl hlori) ν = (toxyl) ν = (rboxyl) Wvnumbr (m -1 ) Figur S4. FT-IR sptr of () DA n (b) DAA. Th FT-IR sptr of th smpls wr msur t 25 o on Prkin Elmr Sptrum n sptropolrimtr btwn m -1. Th = groups in th rbonyl hlori of DA ppr t ν = 1730m -1, whrs th = groups in th rboxyl ws not shift t 1670 m -1, initing tht ll rboxyl groups in DAA wr onvrt to rbonyl hlori groups. 5. Synthsis of DAA-PLLAs DAA-PLLA49 ws prpr s follows. A totl of 11.2 g of PLLA50 (3.7 mmol) ws issolv in 40 ml of istill ihloromthn n 2 ml of istill pyriin t 0 o for 30 min, n 4 g of DA (14.9 mmol; molr rtio of PLLA50: DA = 1:4) ws thn, stirr t this tmprtur for 1.5 h, n t room tmprtur for 24 h. Aftr th rtion, th prout ws wsh in ph 3 Hl solution, n r-pripitt into thnol by issolution in DM twi. Th yil ws 94 wt%. Th othr DAA-PLLAs wr prpr by n nlogous prour. Th vrg molulr wight of DAA-PLLAs ws trmin in THF by GP (HL8220GP systm with α M n A900P olumns) librt with polystyrn stnrs t flow rt of 0.6 ml min -1. 6

7 Supplmntry Mtril (ESI) for hmil ommunitions This journl is () Th Royl Soity of hmistry Anlysis of hmil strutur Th hmil struturs of DAA-PLLAs wr nlyz by FT-IR (Figur S5) n 1 H-NMR (Figur S6) msurmnts. DAA-PLLA120 ν = ν = ν p=φ δ s H 3 (lti) DAA-PLLA79 DAA-PLLA49 DAA-PLLA38 DAA-PLLA Wv numbr (m -1 ) Figur S5. FT-IR sptr of vrious DAA-PLLAs. Th FT-IR sptr of th smpls wr msur t 25 o on Prkin Elmr Sptrum n sptropolrimtr btwn m -1. Th FT-IR sptr of th DAA-PLLAs onfirm th prsn of th vinyln (ν = 1640m -1 ) n phnyl groups (ν p=φ 1504m -1 ) of DAA, n th mthyl group of PLLAs (δ s 1455m -1 ). In ition, th pk intnsity of th vinyl or phnyl group in th DAA-PLLAs vrsus th pk intnsity of th mthyl group in PLLAs rs with rsing omposition of DAA. Ths rsults init tht DA ws sussfully onjugt to th trminl PLLAs. 7

8 Supplmntry Mtril (ESI) for hmil ommunitions This journl is () Th Royl Soity of hmistry 2008 Dl 3 b b ppm Figur S6. Rprsnttiv 1 H-NMR sptrum of DAA-PLLA49. Th 1 H-NMR sptr of vrious DAA-PLLAs wr msur with NMR sptromtr (JEL FX 400) t 400 MHz. Th 1 H-NMR hmil shifts in prts pr million (ppm) wr ror ownfil from 0.00 ppm using ttrmthylsiln (TMS) s n intrnl rfrn. Th solvnt ws Dl 3. Th 1 H-NMR signls of DAA-PLLAs show th prsn of DAA n PLLA in th opolymrs. Th omposition of PLLA or DAA in th DAA-PLLAs ws lult by th pk r rtio of th vinyln protons () in DAA n th -H protons (b) in PLLAs Solubility of PLLAs n DAA-PLLAs Solubility of PLLAs n obtin DAA-PLLAs ws vlut using vrious solvnts. Th smpls wr issolv in vrious solvnts with 1 mg/ml onntrtion Tbl S2 Solubility of PLLAs n DAA-PLLAs LLA unit in PLLAs LLA unit in DAA-PLLAs Solvnts Wtr Mthnol Ethnol Aton Atonitril DMF Pyriin NMP DMS Tolun Hxn DM THF hloroform Mrks " " n " " mn solubl n insolubl, rsptivly. 8

9 Supplmntry Mtril (ESI) for hmil ommunitions This journl is () Th Royl Soity of hmistry 2008 for fw hours. As shown in Tbl S2, solubility of DAA-PLLAs ws intil to PLLA of th sm molulr wight Thrml proprtis of PLLAs n DAA-PLLAs Thrml proprtis of PLLAs n DAA-PLLAs wr nlyz by DS msurmnt (EXSTAR6100, Siko Instrumnts In.) n TGA msurmnt (Q500, TA Instrumnt-Dupont) Anlysis of DS Th mlting tmprtur (T m ) n rystlliztion tmprtur (T ) of PLLAs n DAA-PLLAs wr stimt t hting n ooling rts of 10 o min -1. n smpl msurmnt ws rri out ovr two yls of hting or ooling. Figur S7 shows DS urvs of ll DAA-PLLAs n PLLAs. Th T m of DAA-PLLA ws highr thn tht of PLLA with th sm molulr wight. ) b) 106 o LLA112 DAA-PLLA o LLA o DAA-PLLA o Eno Exo LLA50 LLA36 91 o 156 o 153 o DAA-PLLA49 DAA-PLLA o 103 o 147 o 168 o 158 o 91 o 148 o DAA-PLLA o 157 o LLA o 137 o Tmp. ( o ) Tmp. ( o ) Figur S7. DS urvs upon son hting of () PLLAs n (b) DAA-PLLAs. 9

Supplmntry Mtril (ESI) for hmil ommunitions This journl is () Th Royl Soity of hmistry 2008 5-3-2.

rystllinity of PLLAs n DAA-PLLAs Smpls t onntrtion of 30 mg ml -1 in hloroform wr st onto glss slis.

10 Supplmntry Mtril (ESI) for hmil ommunitions This journl is () Th Royl Soity of hmistry Anlysis of TGA Th thrml grtion bhvior of th smpls ws obsrv from th TG urvs by hting from 80 o to 500 o t rt of 20 o min -1 unr nitrogn tmosphr with flow rt of 200 ml min rystllinity of PLLAs n DAA-PLLAs Smpls t onntrtion of 30 mg ml -1 in hloroform wr st onto glss slis. Thy wr thn ri t room tmprtur for 24 h, n msur ftr nnling t 100 o for 1h by WAXD msurmnt (X-ry iffrtomtr (RINT UltrX18), quipp with sintilltion ountr) using ukα rition (40 kv, 200 ma; wvlngth = Å). (Figur S8). Th rystls of DAA-PLLAs wr intil with PLLAs; i.. DAA i not influn th rystl proprtis of PLLA. () (b) θ (g) Figur S8. Rprsnttiv WAXD pttrns n iffrntil intrfrn mirosopy (DIM) of () DAA-PLLA49 n (b) PLLA Photortivity of PLLAs n DAA-PLLAs DAA-PLLA16, DAA-PLLA38, DAA-PLLA49, DAA-PLLA79 n DAA-PLLA120 wr issolv in DMF to onntrtions of 0.08 mg ml -1, 0.18 mg ml -1, 0.25 mg ml -1, 0.4 mg ml -1 n 1.8 mg ml -1, rsptivly. A glss-filtr 10

11 Supplmntry Mtril (ESI) for hmil ommunitions This journl is () Th Royl Soity of hmistry 2008 high-prssur Hg Lmp (λ > 280 nm, 56 mw m -2 ) ws irrit. Th tim ours of th photortion onvrsion ws monitor by UV-visibl bsorption sptrosopy of th opolymr solutions using HITAHI U3010 Sptrophotomtr. Th ylobutn formtion vi UV-irrition ws tt by 1 H-NMR msurmnt (Figur S9). Smll signls ppr in th hmil shift rng of ppm upon UV irrition, supporting th formtion of n liphti group (ylobutn) substitut by th bnzn ring or rbonyls. () ylobutn (b) ppm Figur S9. Rprsnttiv 1 H-NMR sptr of DAA-PLLA49 () ftr UV irrition for 90 min. n (b) bfor UV irrition Molulr wight hng of PLLAs n DAA-PLLAs by UV irrition. Molulr wight hng of smpls ftr UV irrition t λ > 280 nm ws msur by GP nlysis. Figur S10 shows GP profils of DAA-PLLA49 bfor n ftr UV irrition. Th lution tim of th smpl of ftr UV irrition shift to rlir thn tht bfor UV irrition. In othr wors, imriztion of th PLLA moluls h ourr upon th photortion of trminlly-onjugt DAA. 11

12 Supplmntry Mtril (ESI) for hmil ommunitions This journl is () Th Royl Soity of hmistry 2008 Aftr 90 min UV Mn=5450, Mw/Mn=2.5 Bfor UV Mn=3690, Mw/Mn= [min] Figur S10. Rprsnttiv GP hrts of DAA-PLLA49 bfor n ftr UV irrition for 90 min. (λ > 280 nm, 56 mw m -2 ) Photo-onjugtion of fluorsnt y onto PLLAs n DAA-PLLA films Synthsis of DHA onjugt Alx fluor555 H 2 N S 3 S 3 + NH 2 H 2 N S 3 S 3 + NH 2 H WS 2 N N + r.t.- 24 h H H NH DHA NH (H 2 ) 5 (H 2 ) 5 NH 2 Alx fluor 555 vrin, isoium slt (y) NH H H Shm S4. Rtion of th y n DHA. Dy/DHA A totl of 0.72 mg of DHA (4 μmol) ws issolv in 0.42 ml of PBS buffr (ph = 7.4), n thn 0.76 mg of WS (4 μmol) ws n stirr t room tmprtur for 10 min. Nxt, 1 mg of Alx fluor 555 vrin isoium slt (y) ws, n 12

13 Supplmntry Mtril (ESI) for hmil ommunitions This journl is () Th Royl Soity of hmistry 2008 th rtion ws rri out t room tmprtur for 24 h. Aftr this rtion, th prout ws ilyz in wtr for 3 ys to purify it, n frz-ri for 2 ys Photo-onjugtion mtho of th fluorsnt y onto th films DAA-PLLA38 or PLLA36 films wr prpr by sting 100 μl of th smpls issolv in DM (10 mg ml -1 ) onto glss slis, n thn ri t room tmprtur for 2 ys. Nxt, 0.5 ml of y/dha issolv in PBS buffr (ph = 7.4, wt%) ws ropp onto th films, n xpos to UV light t λ > 280 nm for 100 min. Aftr th UV irrition, th films wr wsh with pur wtr to rmov ny unrt y/dha, n obsrv by onfol fluorsn snning mirosopy. 13

ph controlled assembly of a polybutadiene poly(methacrylic acid) copolymer in water: packing considerations and kinetic limitations

ph controlled assembly of a polybutadiene poly(methacrylic acid) copolymer in water: packing considerations and kinetic limitations Supplmtry Mtril (ESI) for Soft Mttr This jourl is Th Royl Soity of hmistry 2009 p otroll ssmly of polyuti poly(mthryli i) opolymr i wtr pkig osirtios kiti limittios hristi Fryhough, Athoy J. Ry, Giuspp