Supplementary Information. Supplementary Figures

Transcription

1 upplementary Information upplementary Figures m/z upplementary Figure. Mass spectrum of the matrix α-cyano-4-hydroxycinnamic acid (CHCA) used in MALDI-FTICR M in this study.

2 a m/z b.07u = u.07u u u m/z upplementary Figure. MALDI-FTICR M of the first block PDMA (a) Mass spectrum of the first block during the synthesis of the dodecablock copolymer a obtained by iterative RAFT polymerization. (b) enlargement of the corresponding spectrum. The different populations numerated - are presented in the upplementary Table, circles represent α,ω-difunctional chains cationise a + ; stars represent α,ω-difunctional chains doubly cationise a + ; triangles represent fragmented α-functional chains cationise a + generated during the analysis).

3 a m/z b - 4.0u = -AM +DMA -4.08u = -AM 4.0u = +AM -DMA 4.08u = +AM u H 4.0u H a+ 4.0u a u H a m/z upplementary Figure. MALDI-FTICR M of the diblock PDMA -b-pam (a) Mass spectrum of the second block (PDMA -b-pam ) during the synthesis of the dodecablock copolymer a obtained by iterative RAFT polymerization; (b) enlargement of the corresponding spectrum. The different populations numerated - are presented in the upplementary Table 4,

4 circles represent α,ω-difunctional chains cationise a + ; stars represent α,ω-difunctional chains doubly cationise a + ; triangles represent fragmented α-functional chains cationise a + generated during the analysis).

5 a m/z b u = u 8.08u u m/z upplementary Figure 4. MALDI-FTICR M of the st block PBA 5 (a) Mass spectrum of the first block during the synthesis of the hexablock copolymer b obtained by iterative RAFT polymerization; (b) enlargement of the corresponding spectrum. The different populations numerated -4 are presented in the upplementary Table 7, circles represent α,ω-difunctional chains cationise a + ; stars represent α,ω-difunctional chains doubly cationise a + ; triangles represent fragmented α-functional chains cationise a + generated during the analysis, squares represent α,ω-difunctional chains cationise H +.

6 HC block 5 block 5 stat block block stat block H H C4 H H PBA 5 -b-pam 5 -b-p(am 7 -stat-hea )-b-pam 5 -b-p(am 7 -stat-aa 5 )-b-pipam 5 C 80 C 5 C 80 C umber / % (normalized) ize / r.nm upplementary Figure 5. elf-assembly of the hexablock copolymer b (Figure ) in water Dynamic light scattering analysis of the hexablock copolymer b ( mg ml - polymer solution in H ) heated from 5 C to 80 C (transition ) and then cooling down to 5 C (transition ).

7 a u u m/z b u 4.08u u u m/z upplementary Figure 6. MALDI-FTICR M of the first block PAM (a) Mass spectrum of the first block during the synthesis of the icosablock copolymer c obtained by iterative RAFT polymerization; (b) enlargement of the corresponding spectrum. The different populations numerated -6 are presented in the upplementary Table, circles represent α,ω-difunctional chains cationise a + ; stars represent α,ω-difunctional chains doubly cationise a + ; triangles represent fragmented α-functional chains cationise a + generated during the analysis.

8 a u 4.08u m/z b u 4.08u u u m/z upplementary Figure 7. MALDI-FTICR M of the diblock PAM -b-pam (a) Mass spectrum of the diblock copolymer during the synthesis of the icosablock copolymer c obtained by iterative RAFT polymerization; (b) enlargement of the corresponding spectrum. The different populations numerated -6 are presented in the upplementary Table, circles represent α,ωdifunctional chains cationise a + ; stars represent α,ω-difunctional chains doubly cationise a + ; triangles represent fragmented α-functional chains cationise a + generated during the analysis.

9 m/z upplementary Figure 8. MALDI-FTICR M of the triblock PAM -b-pam -b- PDEA Mass spectrum of the triblock copolymer during the synthesis of the icosablock copolymer c obtained by iterative RAFT polymerization; for enlargement of the corresponding spectrum, see upplementary Figure.

10 a H -4.08u = -AM a+ H a+ 4.08u = +AM H 4 a u u m/z b H -.8u = -AM+DEA 4 a+ H a+ H.8u = +AM-DEA 4 a+.8u.8u u u m/z upplementary Figure. MALDI-FTICR M of the triblock PAM -b-pam -b- PDEA (a) Mass spectrum of the triblock copolymer during the synthesis of the icosablock copolymer c obtained by iterative RAFT polymerization; (b) enlargement of the corresponding spectrum. The different populations numerated - are presented in the upplementary Table, circles represent α,ω-difunctional chains cationise a + ; stars represent α,ω-difunctional chains doubly cationise a + ; triangles represent fragmented α-functional chains cationise a + generated during the analysis.

11 m/z upplementary Figure. MALDI-FTICR M of the tetrablock PAM -b-pam -b- PDEA -b-pam Mass spectrum of the tetrablock copolymer during the synthesis of the icosablock copolymer c obtained by iterative RAFT polymerization; for enlargement of the corresponding spectrum, see upplementary Figure.

12 a -4.08u = -AM 4.08u = +AM H a + H a + H 4 a u u m/z b -.8u = -AM+DEA H a +.8u = +AM-DEA H 4 a H 4 a + H 5 a u.8u 5.6 H a u m/z upplementary Figure. MALDI-FTICR M of the tetrablock PAM -b-pam -b- PDEA -b-pam (a) Mass spectrum of the tetrablock copolymer during the synthesis of the icosablock copolymer c obtained by iterative RAFT polymerization; (b) enlargement of the corresponding spectrum. The different populations numerated - are presented in the upplementary Table 4, circles represent α,ω-difunctional chains cationise a + ; stars represent α,ω-difunctional chains doubly cationise a +.

13 m/z upplementary Figure. MALDI-FTICR M of the pentablock PAM -b-pam -b- PDEA -b-pam -b-pdma Mass spectrum of the pentablock copolymer during the synthesis of the icosablock copolymer c obtained by iterative RAFT polymerization; for enlargement of the corresponding spectrum, see upplementary Figure.

14 H H a + C 4 4 H a +.8u = +AM -DEA 8.0u = +DEA -DMA 4.0u = +AM -DMA H 5 a + AD H 4 a + H 0 6 a + AD H 4 a u.8u.8u 8.0u 4.0u m/z upplementary Figure. MALDI-FTICR M of the pentablock PAM -b-pam -b- PDEA -b-pam -b-pdma Enlargement of the spectrum in upplementary Figure (circles represent α,ω-difunctional chains cationise a + ).

15 upplementary Figure 4. ize exclusion chromatography raw data for the icosablock copolymer c. Print screen taken from the software ATRA showing an example of the choice of peak limits for the determination of molecular weight and the dispersity values of the final icosablock copolymer c (0 th block), reported in upplementary Table and in Figure 5b (M n,ec = 4400 g.mol - and Đ =.6). EC was performed using THF as eluent and poly(styrene) as calibration standards.

16 a Response (normalized) umber distribution normalized w(logm) Molecular weight / g.mol - b Response (normalized) umber distribution normalized w(logm) Molecular weight / g.mol - upplementary Figure 5. EC analysis of the final icosablock copolymer. (a) verlay of the EC distribution (w(logm) versus logm) and the number distribution of the final icosablock copolymer c (0 th block) obtained by RAFT polymerization via 0 iterative block extensions; (b) overlay of the EC distribution (w(logm) versus M) and the number distribution of the final icosablock copolymer c.

17 upplementary Tables upplementary Table. Experimental conditions used for the preparation of the dodecablock copolymer a (Figure ) in dioxane at 65 C with AIB as initiator (4h per block) Cycles Monomer DMA AM DEA IPAM DMA AM DEA IPAM DMA AM DEA IPAM DP targeted m monomer added (mg) m CTA added (mg) 44. m AIB added (mg) V dioxane added (ml) V total [a] (ml) m AIB total [b] (mg) [AIB] 0 (x ) (mmol.l - ) [M] 0 (mol.l - ) [CTA] 0 /[AIB] L [c] (%) Cumulative L [d] (%) [a] represent the sum of the volume of the solvent added + volume of the monomer added + V total previous block [b] represent the total weight of AIB at time t 0 considering the weight of AIB added (m AIB added ) + the weight of AIB remaining (m AIB remaining ) from the previous block after 4h (m AIB remaining = m AIB total x fe -kd t x (-f c /) with f=0.5, f c =0, k d =. -5 s - ) [c] theoretical estimation of the fraction of living chains per block (e.g. extendable chain having the Z group) [d] theoretical estimation of the cumulated fraction of living chains

18 upplementary Table. Characterization data for the synthesis of the dodecablock copolymer a in dioxane at 65 C with AIB as initiator (4h per block) Cycles 4 5 Dodecablock copolymer composition Poly(DMA ) Poly(DMA -AM ) Poly(DMA -AM -DEA ) Poly(DMA -AM -DEA -IPAM ) Poly(DMA -AM -DEA -IPAM -DMA ) Monomer conversion [a] (%) M n,th [b] (g mol - ) M n,ec [c] (g mol - ) Đ [c] Cumulative theoretical % of α,ω-difunctional chains [d] > > > > > Poly(DMA -AM -DEA -IPAM -DMA -AM ) > Poly(DMA -AM -DEA -IPAM -DMA -AM - DEA ) > Poly(DMA -AM -DEA -IPAM -DMA -AM - DEA -IPAM ) > Poly(DMA -AM -DEA -IPAM -DMA -AM - DEA -IPAM -DMA ) > Poly(DMA -AM -DEA -IPAM -DMA -AM - DEA -IPAM -DMA -AM ) > Poly(DMA -AM -DEA -IPAM -DMA -AM - DEA -IPAM -DMA -AM -DEA ) > Poly(DMA -AM -DEA -IPAM -DMA -AM - DEA -IPAM -DMA -AM -DEA -IPAM ) > [a] Determined by H MR [b] M n,th = [Monomer] 0 p M Monomer / [CTA] 0 + M CTA (see equation ) [c] determined by EC/RI in DMF with Pty used as molecular weight standards [d] represent the cumulative theoretical percentage of polymer chains having α,ωdual functionalities (R and Z group) after each cycles if only bimolecular terminations by disproportionation occurred (no side reactions)

19 upplementary Table. Poly(,-dimethylacrylamide) homopolymer ( st block) chain structures corresponding to the various peaks in upporting Figure. Peak Theoretical monoisotopic peak Experimental monoisotopic peak tructure

20 upplementary Table 4. PDMA -b-pam diblock copolymer chain structures corresponding to the various peaks in upporting Figure. Peak Theoretical monoisotopic peak Experimental monoisotopic peak H tructure a

21 upplementary Table 5. Experimental conditions used for the preparation of the hexablock copolymer b (Figure ) in dioxane at 65 C with AIB as initiator (4h per block) Cycles Monomer BA AM AM/HEA AM AM/AA IPAM DP targeted m monomer added (mg) m CTA added (mg) m AIB added (mg) V dioxane added (ml) V total [a] (ml) m AIB total [b] (mg) [AIB] 0 (mol.l - ) [M] 0 (mol.l - ) [CTA] 0 /[AIB] L [c] (%) Cumulative L [d] (%) [a] represent the sum of the volume of the solvent added + volume of the monomer added + V total previous block [b] represent the total weight of AIB at time t 0 considering the weight of AIB added (m AIB added ) + the weight of AIB remaining (m AIB remaining ) from the previous block after 4h (m AIB remaining = m AIB total x fe -kdt x(-f c /) with f=0.5, f c =0, k d =. -5 s - ) [c] theoretical estimation of the fraction of living chains per block (e.g. extendable chain having the Z group) [d] theoretical estimation of the cumulated fraction of living chains.

22 upplementary Table 6. Characterization data for the synthesis of the hexablock copolymer b in dioxane at 65 C with AIB as initiator (4h per block) Cycles Hexablock copolymer composition Monomer conversion [a] (%) M n,th [b] (g mol - ) M n,ec [c] (g mol - ) Đ [c] Cumulative theoretical % of α,ω-difunctional chains [d] Poly(BA 5 ) Poly(BA 5 -AM 5 ) > Poly(BA 5 -AM 5 -(AM 7 -stat-hea )) > Poly(BA 5 -AM 5 -(AM 7 -stat-hea )-AM 5 ) > Poly(BA 5 -AM 5 -(AM 7 -stat-hea )-AM 5 - (AM 7 -stat-aa )) > Poly(BA 5 -AM 5 -(AM 7 -stat-hea )-AM 5 - (AM 7 -stat-aa )-IPAM ) [e].6 [e] 8.0 [a] Determined by H MR [b] M n,th = [M] 0 p M M / [CTA] 0 + M CTA (see equation ) [c] determined by EC/RI in THF with poly(styrene) used as molecular weight standards [d] represent the cumulative theoretical percentage of polymer chains having α,ω dual functionalities (R and Z group) after each cycles if only bimolecular terminations by disproportionation occurred (no side reactions) [e] determined by EC/RI in DMF with poly(styrene) used as molecular weight standard

23 upplementary Table 7. Poly(n-butyl acrylate) homopolymer ( st block) chain structures corresponding to the various peaks in upporting Figure 4. Peak Theoretical monoisotopic peak Experimental monoisotopic peak tructure H H 6 a

24 upplementary Table 8. Experimental conditions used for the preparation of the icosablock copolymer c in H at 70 C with VA-044 as initiator (h per block) (blocks to ). Cycles Monomer AM AM DEA AM DMA AM DEA AM DMA AM DP targeted m monomer added (mg) m CTA added (mg) 68. m VA-044 added (mg) g (purified PAM ) V H added (ml) V dioxane added (ml) % H V total [b] (ml) m VA-044 total [a] (mg) [VA-044] 0 (mol.l - ) [M] 0 (mol.l - ) [CTA] 0/ [VA-044] L [c] (%) Cumulative L [d] (%) [a] represent the total weight of VA-044 at time t 0 considering the weight of VA-044 added (m VA-044 added ) + the weight of VA-044 remaining (m VA-044 remaining) from the previous block after h (m VA-044 remaining = m VA-044 total x e -kdt with k d = s - ) [b] represent the sum of the volume of the solvent added + volume of the monomer added + V total previous block [c] theoretical estimation of the fraction of living chains per block (e.g. extendable chain having the Z group) [d] theoretical estimation of the cumulated fraction of living chains

25 upplementary Table. Experimental conditions used for the preparation of the icosablock copolymer c in H at 70 C with VA-044 as initiator (h per block) (blocks to 0). Cycles Monomer DEA AM DMA AM DEA AM DMA AM DEA AM DP targeted m monomer added (mg) m CTA added (mg) m VA-044 added (mg) V H (ml) V total [b] (ml) m VA-044 total [a] (mg) [VA-044] 0 (mol.l - ) [M] 0 (mol.l - ) [CTA] 0/ [VA-044] L [c] (%) Cumulative L [d] (%) [a] represent the total weight of VA-044 at time t 0 considering the weight of VA-044 added (m VA-044 added ) + the weight of VA-044 remaining (m VA-044 remaining) from the previous block after h (m VA-044 remaining = m VA-044 total x e -kdt with k d = s - ) [b] represent the sum of the volume of the solvent added + volume of the monomer added + V total previous block [c] theoretical estimation of the cumulated fraction of living chains (e.g. extendable chain)

26 upplementary Table. Characterization data for the synthesis of the icosablock copolymer c in H at 70 C with VA-044 as initiator (h per block) Cycles Multiblock copolymer composition Monomer conversion [a] (%) M n,theory [b] (g mol - ) M n,ec [c] (g mol - ) Đ [c] Cumulative theoretical % of α,ω-difunctional chains [d] Poly(AM ) Poly(AM -AM ) Poly(AM -AM -DEA ) Poly(AM -AM -DEA -AM ) Poly(AM -AM -DEA -AM -DMA ) Poly(AM -AM -DEA -AM -DMA - AM ) Poly(AM -AM -DEA -AM -DMA - AM -DEA ) Poly(AM -AM -DEA -AM -DMA - AM -DEA -AM ) Poly(AM -AM -DEA -AM -DMA - AM -DEA -AM -DMA ) Poly(AM -AM -DEA -AM -DMA - AM -DEA -AM -DMA -AM ) Poly(AM -AM -DEA -AM -DMA - AM -DEA -AM -DMA -AM -DEA ) Poly(AM -AM -DEA -AM -DMA - AM -DEA -AM -DMA -AM -DEA AM ) Poly(AM -AM -DEA -AM -DMA - AM -DEA -AM -DMA -AM -DEA AM -DMA ) 4 Poly(AM -AM -DEA -AM -DMA - AM -DEA -AM -DMA -AM -DEA AM -DMA -AM ) 5 Poly(AM -AM -DEA -AM -DMA - AM -DEA -AM -DMA -AM -DEA AM -DMA -AM -DEA ) 6 Poly(AM -AM -DEA -AM -DMA - AM -DEA -AM -DMA -AM -DEA AM -DMA -AM -DEA -AM ) 7 Poly(AM -AM -DEA -AM -DMA - AM -DEA -AM -DMA -AM -DEA AM -DMA -AM -DEA -AM -DMA ) 8 Poly(AM -AM -DEA -AM -DMA - AM -DEA -AM -DMA -AM -DEA - AM -DMA -AM -DEA -AM -DMA AM ) Poly(AM -AM -DEA -AM -DMA - AM -DEA -AM -DMA -AM -DEA - AM -DMA -AM -DEA -AM -DMA AM -DEA ) 0 Poly(AM -AM -DEA -AM -DMA - AM -DEA -AM -DMA -AM -DEA - AM -DMA -AM -DEA -AM -DMA - AM -DEA -AM ) [a] Determined by H MR [b] M n,th = [M] 0 p M M / [CTA] 0 + M CTA (see equation ) [c] determined by EC/RI in THF with Pty used as molecular weight standards [d] represent the cumulative theoretical percentage of polymer chains having α,ω dual functionalities (R and Z group) after each cycles if only bimolecular terminations occurred (no side reactions)

27 upplementary Table. PolyAM homopolymer ( st corresponding to the various peaks in upplementary Figure 6. block) chain structures Peak Theoretical monoisotopic peak Experimental monoisotopic peak tructure

28 upplementary Table. Diblock copolymer chain structures corresponding to the various peaks in in upplementary Figure 7. Peak Theoretical monoisotopic peak Experimental monoisotopic peak tructure

29 upplementary Table. Triblock copolymer chain structures corresponding to the various peaks in upplementary Figure. Peak Theoretical monoisotopic peak Experimental monoisotopic peak tructure

30 upplementary Table 4. Tetrablock copolymer chain structures corresponding to the various peaks in upplementary Figure. Peak Theoretical monoisotopic peak Experimental monoisotopic peak tructure