Supporting information

Transcription

1 Eletroni Supplementary Material (ESI) for Polymer Chemistry. This journal is The Royal Soiety of Chemistry 2016 Supporting information Polymerisation of 2-arylamio-2-methylpropane sulfoni ai soium salt (NaAMPS) an aryloyl phosphatiylholine (APC) via aqueous Cu(0)- meiate raial polymerisation Vasiliki Nikolaou, a Alexanre Simula, a Martijn Droesbeke, a Nuttapol Risangu, a Athina Anastasaki, a,b Kristian Kempe, a,b Paul Wilson, a,b an Davi M. Haleton a,b * a - University of Warwik, Chemistry Department, Library roa, CV4 7AL, Coventry, Unite Kingom. b - ARC Centre of Exellene in Convergent Bio-Nano Siene an Tehnology, Monash Institute of Pharmaeutial Sienes, Monash University (Parkville Campus), 399 Royal Parae, Parkville, Vitoria 3152, Australia Materials All hemials were purhase from Sigma-Alrih or Fisher Sientifi unless otherwise state. The water soluble initiator 2,3-ihyroxypropyl 2-bromo-2-methylpropanoate, an PEG-maroinitiator were prepare as reporte in the literature. 1, 2 Tris(2- (imethylamino)ethyl)amine (Me 6 TREN) was synthesize aoring to literature proeures an store uner nitrogen prior to use. 3 Copper (I) bromie (CuBr), was sequentially washe with aeti ai an ethanol an rie uner vauum. Instruments an analysis 1 H NMR spetra were reore on Bruker DPX-300 an DPX-400 spetrometers using euterate solvents (D 2 O) obtaine from Alrih. Aqueous SEC traes were obtaine on a PL-GPC50 system using a buffer (0.1M NaNO 3, ph 7.4) eluent at 30 C, equippe with a

2 refrative inex etetor, two PLaquagel-OH 30 ( mm), PLaquagel guar ( mm) an autosampler. Narrow linear poly(ethylene oxie) an poly(metharyli ai) stanars in range of 200 to g.mol -1 were use to alibrate the system. All samples were passe through 0.22μm PTFE filter before analysis. General proeure for aqueous SET-LRP To a Shlenk tube fitte with a magneti stirring bar an a rubber septum, H 2 O (2 ml) an Me 6 -Tren (0.4 equiv.) were ae an the mixture was bubble with nitrogen for 15 min. CuBr (0.4 equiv.) was then arefully ae uner slight positive pressure of nitrogen. The mixture immeiately beame blue ([Cu(Me 6 -Tren)]Br 2 ) an a preipitation (Cu(0)) was observe. A separate vial fitte with a rubber septum an magneti stirring bar was harge with initiator (1 equiv.), monomer (DP equiv.) an H 2 O (2 ml). The mixture was left to stir until omplete issolution of the monomer was obtaine prior to eoxygenation by nitrogen sparging for 10 minutes. The solution was then annulate into the Shlenk tube an the reation was left to proee at 0 C. General proeure for hain extension/opolymerisation by aqueous SET-LRP General proeure for homopolymerisation following using the appropriate [M] : [I] : [CuBr] : [Me 6 -Tren] ratio. Homopolymerisations allowe to reah near quantitative onversion prior to aition of a egasse aliquot of the hosen monomer (DP, equiv.), in H 2 O (50 wt%) via a nitrogen-purge syringe. The resulting solution was stirre at 0 C an progress was followe intermittent sampling with analysis by 1 H NMR an SEC.

3 a,b, a b HN SO 3 n O Na (ppm) Figure S1: 1 H NMR (D 2 O) spetrum of PNaAMPS 20 utilising aqueous SET-LRP. Initial onitions: [NaAMPS]:[I]:[CuBr]:[Me 6 -Tren] = [20]:[1]:[0.4]:[0.4] in 4 ml H 2 O at 0 o C wlogm M (g.mol -1 ) Figure S2: Aqueous SEC analysis for the synthesis of PNaAMPS 40 utilising aqueous SET-LRP. Initial onitions: [NaAMPS]:[I]:[CuBr]:[Me 6 -Tren] = [40]:[1]:[0.4]:[0.4] in 4 ml H 2 O at 0 o C.

4 wlogm M (g.mol -1 ) Figure S3: Aqueous SEC analysis for the synthesis of PNaAMPS 80 utilising aqueous SET-LRP. Initial onitions: [NaAMPS]:[I]:[CuBr]:[Me 6 -Tren] = [80]:[1]:[0.8]:[0.4] in 4 ml H 2 O at 0 o C wlogm M (g.mol -1 ) Figure S4: Aqueous SEC analysis for the synthesis of PNaAMPS 160 utilising aqueous SET-LRP. Initial onitions: [NaAMPS]:[I]:[CuBr]:[Me 6 -Tren] = [160]:[1]:[0.8]:[0.4] in 4 ml H 2 O at 0 o C.

5 1.0 wlogm M (g.mol -1 ) Figure S5: Aqueous SEC analysis for the synthesis of PNaAMPS 160 utilising aqueous SET-LRP. Initial onitions: [NaAMPS]:[I]:[CuBr]:[Me 6 -Tren] = [160]:[1]:[1.6]:[1] in 4 ml H 2 O at 0 o C.

6 Table S1. Polymerisation of KSPA by aqueous SET-LRP DP n,th T ( C) Ratio Time Conversion *Ɖ *M n,th (Cu-L) (g.mol -1 ) **M n,nmr *M nsec (g.mol -1 ) (g.mol -1 ) min Full min Full min Full h 97% h 97% * Determine by aqueous SEC ** Determine by 1 H NMR in D 2 O Figure S6: Aqueous SEC analysis for the synthesis of PKSPA utilising aqueous SET-LRP.

7 Figure S7: Aqueous SEC analysis for the synthesis of PAPC utilising aqueous SET-LRP.

8 Table S2. Synthesis of NaAMPS ontaining blok opolymers by aqueous SET-LRP. Cyle Time Conversion *M n (min) (%) (g.mol -1 ) *Đ In situ AMPS 30 > Chain Extension AMPS 30 > PEGA AMPS Blok HEAm (o)polymerisations AMPS AMPS NIPAm * Determine by aqueous SEC a b a,b, a,b, HN SO 3 n O 1 Na ppm) Figure S8: 1 H NMR analysis for the in situ hain extension from a PNaAMPS 20 maroinitiator utilising aqueous SET-LRP. Initial onitions: [NaAMPS]:[I]:[CuBr]:[Me 6 -Tren] = [20]:[1]:[0.4]:[0.4]. Chain extension ahieve upon aition of an aliquot of NaAMPS (20 equiv.) in H 2 O (2 ml).

9 Table S3. Synthesis an hain extension of PAPC pseuo blok opolymers by aqueous SET-LRP. DP n,th T ( C) Ratio (Cu-L) Time Conv. *Ɖ M n,th (g.mol -1 ) **M n,nmr (g.mol -1 ) *M nsec (g.mol -1 ) min 92 % h30 Full h30 Full h30 76 % * Determine by aqueous SEC ** Determine by 1 H NMR in D 2 O Figure S9: Aqueous SEC analysis for the synthesis an hain extension of PAPC pseuo blok opolymer utilising aqueous SET-LRP. Numbers reporte ome from analysis of the peaks in the box. The low moleular weights peaks i not oinie with the monomer an have been assigne as unientifie impurities/system peaks.

10 Table S4. Synthesis PEG-b-NaAMPS opolymers by aqueous SET-LRP. DP Cu:L *M n,nmr (g/mol) **M n,sec (g/mol) M n,th (g/mol) **Ɖ Conversion (%) : : : * Determine by 1 H NMR in D 2 O ** Determine by aqueous SEC Figure S10: Aqueous SEC analysis for the synthesis of PEG-b-NaAMPS opolymer by aqueous SET-LRP.

11 a b a' b',e O OHN O e O 7/8 g SO 3 Na f,e a,b,a,b,f a,b ppm) Figure S11: 1 H NMR analysis for the in situ hain extension from a PPEGA 10 maroinitiator utilising aqueous SET-LRP. Initial onitions: [PEGA]:[I]:[CuBr]:[Me 6 -Tren] = [10]:[1]:[0.4]:[0.4]. Chain extension ahieve upon aition of an aliquot of NaAMPS (20 equiv.) in H 2 O (2 ml). a b a' b' HN OHN O OH g SO 3 Na f a,b a,b,a,b,f 1,g (ppm) Figure S12: 1 H NMR analysis for the in situ hain extension from a PHEAm 20 maroinitiator utilising aqueous SET-LRP. Initial onitions: [HEAm]:[I]:[CuBr]:[Me 6 -Tren] = [20]:[1]:[0.4]:[0.4]. Chain extension ahieve upon aition of an aliquot of NaAMPS (20 equiv.) in H 2 O (2 ml).

12 HN a b a' b' OHN O a,b, SO 3 e f Na a,b,,a,b,f 1 e (ppm) Figure S13: 1 H NMR analysis for the in situ blok opolymerisation from a PNaAMPS 20 maroinitiator utilising aqueous SET-LRP. Initial onitions: [NaAMPS]:[I]:[CuBr]:[Me 6 -Tren] = [20]:[1]:[0.4]:[0.4]. Chain extension ahieve upon aition of an aliquot of NIPAm (20 equiv.) in H 2 O (2 ml) wlogm M (g.mol -1 ) Figure S14: SEC analysis for the PNaAMPS 20 maroinitiator utilising aqueous SET-LRP. Initial onitions: [NaAMPS]:[I]:[CuBr]:[Me 6 -Tren] = [20]:[1]:[0.4]:[0.4].

13 Table S5. Synthesis of P(APC) 10 -b-(nipam) 80 by aqueous SET-LRP. DP n,th T ( C) Ratio (Cu-L) Time Conv. *Ɖ M n,th (g.mol -1 ) **M n,nmr (g.mol -1 ) *M nsec (g.mol -1 ) h 97 % * (10) * h 96 % * * * Determine by aqueous SEC ** Determine by 1 H NMR in D 2 O g a b a b,e f g a,b e h i,e h f a,b,a,b,i f g Figure S15: 1 H NMR analysis for the in situ blok opolymerisation from a PAPC maroinitiator utilising aqueous SET-LRP. Initial onitions: [APC]:[I]:[CuBr]:[Me 6 -Tren] = [10]:[1]:[0.4]:[0.4]. Copolymerisation ahieve upon aition of an aliquot of NIPAm (80 equiv.) in H 2 O (2 ml).

14 Figure S16: DLS ata for P(APC) 10 -b-(nipam) 80 in pure water at 20 C (left) an above the LCST at 50 C (right) showing temperature epenent transition to well efine nanopartiles. Figure S17: DLS ata for heating-ooling yles of the P(APC) 10 -b-(nipam) 80 in pure water.

15 Referenes 1. S. Perrier, S. P. Armes, X. S. Wang, F. Malet an D. M. Haleton, Journal of Polymer Siene Part A: Polymer Chemistry, 2001, 39, S. Perrier an D. M. Haleton, European Polymer Journal, 2004, 40, M. Ciampolini an N. Nari, Inorgani Chemistry, 1966, 5,