Supporting Information

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1 Supporting Informtion ICGM, ENSCM, Univ Montpellier, CNRS, Cedex 5, Montpellier, Frne L-LA monomer ws kindly gifted y Pur nd purified y stirring in dry diethyl ether followed y rerystlliztion in dry toluene. The solid ws kept under nitrogen. 1-utnol (Crlo Er) ws dried over CH 2, then distilled nd kept over 4Å moleulr sieves under nitrogen. All dried solvents were otined from drying olumns using setup from MBrun SPS nd were olleted dily, exept for nhydrous grde etonitrile supplied y Sigm nd used s reeived. 1,5,7-Triziylo[4.4.]de-5- ene (TBD) (98 % purity), 2-hloro-4,4,5,5-tetrmethyldioxphospholne (TMDP) (95 % purity), hromium(iii) etyletonte (97 % purity), ylohexnol (> 99 % purity) nd sodium tetrphenylorte (> 99.5 % purity) were supplied from Sigm Aldrih nd ketoprofen (98% purity) ws supplied from TCI hemil. All hemils were used s reeived unless mentioned otherwise. TBDH +.keto - ws synthesized following proedure desried erlier 1 nd ws refully dried in vuum oven overnight (6 C, 1-2 mr) just efore use to get yellow powder. TBDH +.BPh 4 - ws synthesized ording to the proedure reported y Sun et l.. 2 Photopolymeriztions were onduted in qurtz Shlenk tue of 1 m dimeter (previously flmed) nd under nitrogen. L-LA nd the PBG were introdued in the retor nd sumitted to three vuum/nitrogen yles. Then the 1-utnol inititor ws dded, followed y the dry solvent. The retor ws equipped with septum llowing to liquot. Irrdition ws performed in Ryonet RPR2 (with 12 lmps t 254 nm) during 1 minutes. The liquots were quenhed with enzoi id (3 eq. versus TBDH +.keto - dissolved in CH 2 Cl 2 ) efore eing nlyzed y 1 H NMR. The polymer produt ws isolted y preipittion of the retion medi in old diethyl ether followed y filtrtion. Supplementry polymeriztions were performed with pure TBD tlyst in the presene of either 1- utnol or wter. (Tle S2, entries 2-3). A PLA initited y 1-utnol ws synthesized with similr proedure s reported efore. A solution with.4 M of TBD nd.55 M of 1-utnol ws prepred..5 g (3.5 mmol) of L-LA ws dded to previously flmed Shlenk nd sumitted to three vuum/nitrogen yles. 2.5 ml of dihloromethne ws dded in order to soluilize the monomer. Then.1 ml of the solution ontining TBD nd 1-utnol ws dded. The retion mixture ws llowed to stir for 2 min efore eing quenhed with enzoi id (3 eq versus TBD). The polymer produt ws isolted y preipittion of the retion medium in old diethyl ether followed y filtrtion. For PLA initited y wter (no lohol ws dded to the solution), 4 µl (4 mg,.22 mmol) of wter ws dded diretly to the soluilized monomer, nd the retion ws quenhed 2 min fter the ddition of TBD solution. The polymer ws reovered using the sme preipittion proedure. Nuler Mgneti Resonne (NMR) ws performed on Bruker AV spetrometer (4 Hz) to reord 1 H NMR spetr in CDCl 3 (purhsed from Eurisotop). Monomer onversions of L-LA were lulted y ompring the reltive intensity of the pek t 5. ppm orresponding to the CH of the monomer with the intensity of the signl t 5.1 ppm ttriuted to the CH of the polymer. 1

2 Phosphityltion experiments were performed following the proedure reported y Spyros et l. 3 A stok solution ws prepred y dissolving 255 mg of hromium(iii) etyletonte (Cr() 3 ) nd 73 mg of ylohexnol (internl stndrd) in 25 ml of pyridine:cdcl 3 solvent mixture (2.3:1 v/v), proteted from moisture using 4 Å moleulr sieves. 2 3 mg of polymer smple ws dissolved in.6 ml of stok solution in n NMR tue, efore dding 6 mg of 2-hloro-4,4,5,5-tetrmethyldioxphospholne (TMDP). The mount of ll the retnts should e known urtely. The mixture ws left to ret for 3 minutes t room temperture efore quiring the 31 P-NMR spetr, using Bruker AV 4 MHz spetrometer (128 sns). The inverse gted deoupling tehnique ws used with 3 seonds dely time. Spetr were referened in reltion to the produt of TMDP reted with wter, t δ = ppm. Clssil end groups of liner PLA i) CH(CH 3 )OH ii) -COOH (if initited y wter) nd ylohexnol ret with TMDP to give phosphorous dduts visile t 146.5, nd 146 ppm respetively. Size exlusion hromtogrphy (SEC) ws performed in tetrhydrofurn (THF) t flow rte of 1. ml/min t 3 C. An Agilent PLgel 5 µm gurd olumn nd two olumns 5 µm PLgel Mixed D onneted in series were used. Vrin 39-LC visometer detetor, Vrin 39-LC refrtive index detetor, UV detetor (t 254 nm) nd Polymer Lortories utosmpler were employed. Dt quisition nd lultions were performed using Cirrus Multi GPC/SEC softwre. Universl lirtion ws done with PS stndrds from Agilent Tehnologies (EsiVil) dissolved t known onentrtion nd using the intrinsi visosities given y the supplier. PLA smples were dissolved in THF t pproximtely 3 mg.ml -1 nd dn/d of.46 ml.g -1 4 ws pplied to nlyze the results. MALDI-TOF nlyses were performed on Bruker Ultrflex III mss spetrometer using nitrogen lser for MALDI (λ = 337 nm). Mss spetr of 25 shots were umulted in positive mode for the spetr t 25 kv elertion voltge nd refletron lens potentils t 26.3 KV. Mixture of peptides ws used for externl lirtion. Polymer smples were dissolved in dihloromethne t onentrtion of 1 mg.ml -1. The tioniztion gent used ws NI dissolved in MeOH t onentrtion of 1 mg.ml -1. The mtrix used ws dithrnol nd ws dissolved in dihloromethne t onentrtion of 1 mg.ml -1. Solutions of mtrix, slt, nd polymer were mixed in volume rtio of 3:1:1 respetively. The mixed solution ws hnd-spotted on MALDI trget nd left to dry. Photodegrdtion of NBPh 4 hs never een reported in dihloromethne, whih is possile explntion for the filure of the photopolymeriztion using TBDH +.BPh 4 - in this solvent (Tle S1, entry 1). In etonitrile, the solvent generlly used for the photohemil study of NBPh 4, the polymeriztion ourred fter 1 min of irrdition ut plteu ws rehed t round 6 % monomer onversion, proly due to the insoluility of the polymer (Tle S1, entry 2). A 5:5 mixture of the two solvents did not help to overome this plteu (Tle S1, entry 3). 2

3 d ) d d Ar e f Ar CD 2 Cl 2 + f e e e f f ) ) d) 3

4 Intens. [.u.] Intens. [.u.] Intens. [.u.] ) [(C 3 H 4 O 2 ) 41 N ]+ Simulted ) m polymer Mn,SEC I [ COOH] I[ylohexnol I [ CHCH 3 OH] I [ylohexnol 4

5 ln M ln [n] 12,5 12,3 12,1 11,9 11,7 11,5 11,3 11,1 1,9 1,7 1,5 1, ,5 12 Elution time(min) ),6,4,2 -,2 -,4 -,6 -, , ,5 12 ) ln M 5

6 U.A. U.A. d,d e,e f,f Et2O Et2O d,d f,f d e f f e d g CDCl 3 ) g ) 9,9 7,9 BuOPLAH RI 5,9 3,9 1,9 -, Elution time (se) BuOPLAH UV 8,8 7,8 6,8 5,8 TBD PLAH UV TBD PLAH RI 4,8 3,8 2,8 1,8,8 -, Elution time (se) 6

7 Simulted ) 7

8 8

9 [.u.] Intens. [.u.] Intens. [.u.] Intens. [ Intens. [.u.] Intens. [.u.] Intens. [.u.] EPT22_1mL :O13 MS Rw EPT213_1mL :O22 MS Rw EPT213_1mL :O22 MS Rw Simulted Simulted = 1.69, onv = 1%, M n,theo = [L LA] [H 2 O] M L LA onv (%) = 2 45 g/mol ) x EPT8-SR_preipite_medium :D23 MS Rw x14 18EPT6-SR_medium :D2 MS Rw Simulted Simulted x EPT8-SR_preipite_medium :D23 MS Rw [L LA] [ketoprofente] M L LA onv (%)+ M ketoprofente = 2 7 g/mol, onv = 16% (1) Arimitsu, K.; Endo, R. Applition to Photoretive Mterils of Photohemil Genertion of Superses with High Effiieny Bsed on Photoderoxyltion Retions. Chem. Mter. 213, 25 (22), (2) Sun, X.; Go, J. P.; Wng, Z. Y. Biyli Gunidinium Tetrphenylorte: A Photose Genertor nd A Phototlyst for Living Anioni Ring-Opening Polymeriztion nd Cross-Linking of Polymeri Mterils Contining Ester nd Hydroxy Groups. J. Am. Chem. So. 28, 13 (26), (3) Spyros, A. Quntittive Determintion of the Distriution of Free Hydroxyli nd Croxyli Groups in Unsturted Polyester nd Alkyd Resins y31p-nmr Spetrosopy. J. Appl. Polym. Si. 22, 83 (8), (4) Zhng, X.; Wymouth, R. M. Zwitterioni Ring Opening Polymeriztion with Isothioures. ACS Mro Lett. 214, 3 (1),