Supporting Information. preparation of polyion complex micelles

Transcription

1 Supporting Information Synthesis of ouble hyrophilic block copolymers an inuce assembly with oligochitosan for the preparation of polyion complex micelles J. Reboul, a T. Nugay, a N. Anik, b H. Cottet, b V. Ponsinet c, M. In, P. Lacroix-Desmazes,* a C. Gérarin* a a Institut Charles Gerhart - UMR5253 CNRS/UM2/ENSCM/UM1, Ecole Nationale Supérieure e Chimie e Montpellier, 8 rue e l Ecole Normale, Montpellier Ceex 5, France b Institut es Biomolécules Max Mousseron (IBMM, UMR 5247 CNRS UM1/UM2), place Eugène Bataillon, case courrier 176, 3495 Montpellier Ceex5, France c Centre e Recherche Paul Pascal, 115 avenue Schweitzer 33 6 Pessac, France Laboratoire es colloïes, verres et nanomatériaux (LCVN)- UMR 5587 CNRS-UM2, Université Montpellier II, place Eugène Bataillon, 3495 Montpellier Ceex 5, France. CORRESPONDING AUTHOR FOOTNOTE: Patrick Lacroix-Desmazes, tel.: (+33) ; fax: (+33) ; aress: patrick.lacroix-esmazes@enscm.fr; Corine Gérarin, tel.: (+33) ; fax: (+33) ; aress: corine.gerarin@enscm.fr 1

2 1 H NMR spectra PEO macroinitiator: O CH a b c 3 C H O-( 2 C H 2 O)-C H 2 C H 2 -O-C-C-Br m b a c δ (ppm) Figure S1. 1 H NMR spectrum of the PEO macroinitiator in CDCl 3. PEO-b-PtBuA: a b c O O-(CH 2 CH 2 O)-CH 2 CH 2 -O-C-C ( CH 2 -CH ) Br m C O g e f O H 3 C C n b g c a f e δ (ppm) Figure S2. 1 H NMR spectrum of PEO113-b-PtBuA33 (iblock copolymer 4 in Table 1) in CDCl 3. 2

3 PEO-b-PAA: a b c O e f O-(CH 2 CH 2 O)-CH 2 CH 2 -O-C-C- ( CH 2 -CH ) Br m C O n b DMSO OH c a f e δ (ppm) Figure S3. 1 H NMR spectrum of PEO113-b-PAA33 (iblock copolymer 4 in Table 2) in DMSO- 6. Determination of effective charge ensity of PAA 129 -PEO 5, PAA 65 - PEO 2 an PAA 46 -PEO 2 iblock copolymers Correcte Area (mau) Probe ion PAA 129 PEO 5 PAA 65 PEO 2 PAA 46 PEO C M,1 (mm) Figure S4: Calibration curves obtaine by inirect UV etection CE for iblock copolymers. Electrophoretic conitions as in figure 2. C M,1 is the molar concentration of charge monomers (AA). Each ata point is the average of nine measurements. Least square regression equations: y=2.61x (r 2 =.989) for f=.16; y=2.96x (r 2 =.995) for f=.13; y=2.67x (r 2 =.984) for f=.58. 3

4 Dynamic Light Scattering analysis of copolymers an oligochitosan stuie iniviually as a function of ph. 8 Scattere intensity (Kcps) ph Figure S5. Scattere intensity of an aqueous solution of PEO113-b-PAA33 iblock copolymer (circles) or oligochitosan (iamons) analyze iniviually as a function of the ph of the solution. 4

5 Depenence of ionization egrees of the PAA block (a weak polyaci) an of oligochitosan (a weak polybase) with ph 1 POE114-b-PAA33 Oligochitosan,8,6 α,4, ph Figure S6. Theoretical epenence of the ionization egrees of the PAA block an oligochitosan with ph. Effect of salt concentration on the existence of the complex micelles 1,2 1,8,6,4,2,2,4,6,8 1 1,2 C NaCl (mol/l) Figure S7: Normalize intensity as a function of NaCl concentration (mol.l -1 ) for the PEO113-b-PAA33/oligochitosan complex system. 5

6 (a) (c) (b) (b) Hyroynamic iameter (nm) Hyroynamic iameter(nm) Figure S8: Size istribution of aggregates forme at ph=6 with the PEO113-b- PAA33/oligochitosan complex system before salt aition, (b) after salt aition an (c) after removal of salt by ialysis. 6

7 Effect of block length variation on complex micelle morphology. Scaling relationships ,8,6,4, ph Figure S9: Scattere intensity, hyroynamic iameter an polyispersity inexes plotte as a function of ph for mixtures compose of iblock copolymers with DP PAA = 9 (crosses), 22 (empty squares) an 33 (triangles). 7

8 Cohen Stuart qualitatively stuie the effect of block length variation on complex micelle morphology 1 by making analogies with hyrophobically associating systems for which scaling relationships have been etermine. 2,3 For micelles compose of strongly asymmetric iblock copolymers with a neutral-hyrophobic architecture, two critical cases can be istinguishe epening on the length of the neutral (hyrophilic) an hyrophobic blocks : starlike micelles are obtaine when DPcorona >> DPcore, they are constitute of a very small core compare to the overall imensions of the micelles; an crew-cut micelles are obtaine when DPcore>>DPcorona, in that case, the micellar imensions are ominate by the size of the core. In both cases, the block length ratio governs the physics of the micellization process, the aggregation number an micelle raius. In the case of starlike micelles, the value of the aggregation number N agg at the equilibrium is given by Equation S1 1 : N agg ~ (DP core γ) 4/5 (ln R corona R core ) -6/5 Equation S1 With γ the interfacial tension between the core an the solvent an R corona an R core the raii of corona an core respectively. In the case of crew-cut micelles, Equation S2 hols 1 : N agg ~ DP core 2 γ 7/11 DP corona -18/11 υ -6/11 Equation S2 With υ the solvent quality for the corona blocks. 1 M. A. Cohen Stuart, N. A. M. Besseling an R. G. Fokking, Langmuir, 1998, 14, A. Halperin an S. Alexaner, Macromolecules, 1989, 22, O. V. Borisov an E. B. Zhulina, Macromolecules, 22, 35,