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Supporting Information Amphiphilic PEG-‐b-‐PFPE-‐b-‐PEG triblock copolymer: Synthesis by
CuAAC click chemistry and self-‐assembly in water
Gérald Lopez, Marc Guerre, Judith Schmidt, Yeshayahu Talmon, Vincent Ladmiral, Jean-‐Pierre Habas, and Bruno Améduri
RMN)19F)LG=14)vs)Z=DOL)
O O O O O
F F F F F F
F F F Fm n
LG-14
HO O O O OH
F F F F F F
F F F Fm n
Fomblin® Z-DOLa
a
a’
a’
b’
b’
c’
c’
x
x x
x
Figure S1. 1H NMR spectra overlay of poly(tetrafluoroethylene oxide-‐co-‐difluoromethylene oxide)-‐α,ω-‐diol (Fomblin® Z-‐DOL, bottom spectrum) and PFPE-‐diyne 1 (top spectrum) recorded in CD3OD.
Stratégie)2):)propargyla'on)du)Z=DOL)
νOH
νCH
HO O O O OH
F F F F F F
F F F Fm n
O O O O O
F F F F F F
F F F Fm n
Br
NaOHCH3CN / THF55 °C, 2 jours
Rdt. 82 %LG-14Z-DOL
O O O O O
F F F F F F
F F F Fm n
LG-14
HO O O O OH
F F F F F F
F F F Fm n
Fomblin® Z-DOL
Figure S2. FTIR spectra overlay of poly(tetrafluoroethylene oxide-‐co-‐difluoromethylene oxide)-‐α,ω-‐diol (Fomblin® Z-‐DOL, bottom spectrum) and PFPE-‐diyne 1 (top spectrum).
Electronic Supplementary Material (ESI) for Polymer Chemistry.This journal is © The Royal Society of Chemistry 2015
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a
× MeOH
× MeOH
2
OO
N3 p
a
Figure S3. 1H NMR spectrum of PEG-‐azide 2 recorded in CD3OD.
RMN)1H)LG=14)
13"
O O O O O
F F F F F F
F F F Fm n
LG-14
a
a
b
b
c
c
× MeOH
Figure S4. 1H NMR spectrum of PFPE-‐diyne 1 recorded in CD3OD.
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O O O O O
F F F F F F
F F F Fm n
LG-14
Figure S5. 19F NMR spectra overlay of PEG-‐b-‐PFPE-‐b-‐PEG triblock copolymer (top spectrum) and PFPE-‐diyne 1 (bottom spectrum) recorded in CD3OD.
Figure S6. FTIR spectra overlay of PEG-‐b-‐PFPE-‐b-‐PEG triblock copolymer (blue spectrum) and PEG-‐azide 2 (red spectrum).
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Créé avec le logiciel Proteus de NETZSCH
[#] Type[1.4] Dynamique
Gamme 200/10.0(K/min)/-150
Vitesse d´acq300.00
STC1
SR0
LN21.0
Corr.---
[#] Type[1.5] Dynamique
Gamme-150/10.0(K/min)/ 200
Vitesse d´acq300.00
STC1
SR0
LN2désactivé
Corr.---
Projet :Identité :Date / temps d'heure :Laboratoire :
gl16/04/2015 14:11:59IAM
Opérateur :Échantillon :Référence :Matériau :
glPEG-PFPE-PEG(2), 12.71 mg
polymères
Corr./Cal.temp :Fich.sens :Porte-éch./TC :Mode/Type de mes. :
/ CAL23072013.ngb-td5SENS23072013.ngb-ed5DSC 200F3 t-sensor / EDSC / Échantillon
Segments :Creuset :Atmosphère :Gamme m. :
5Pan Al, pierced lid
5000 µV
Instrument : NETZSCH DSC 200F3 240-20-0098-L Fichier : C:\NETZSCH\Proteus6\data\gerald\PEG-PFPE-PEG(2).ngb-sd5
-100.0 -50.0 0.0 50.0 100.0 150.0 200.0Température /°C
-3
-2
-1
0
1
2
3
DSC /(mW/mg)
Principal 2015-04-16 17:52 Utilisateur: Utilisateur DSC
111.1 J/g27.6 °C23.4 °C
Pic complexe: Aire:Pic:Onset:
-109.9 J/g57.1 °C51.0 °C
Pic complexe: Aire:Pic:Onset:
[1.5][1.4]
↑ exo
Figure S7. DSC thermogram for PEG-‐b-‐PFPE-‐b-‐PEG triblock copolymer.
Créé avec le logiciel Proteus de NETZSCH
Projet :Identité :Date / temps d'heure :Laboratoire :Opérateur :
genomegl12/05/2015 14:01:32IAMgl
Échantillon :Référence :Matériau :Corr./Cal.temp :Fich.sens :
PEG-N3, 1.37 mgpierced Al pan,0 mgpolymères / CAL23072013.ngb-td5SENS23072013.ngb-ed5
Gamme :Porte-éch./TC :Mode/Type de mes. :Segments :Creuset :
-150/10.0(K/min)/ 150DSC 200F3 t-sensor / EDSC / Échantillon5/5Pan Al, pierced lid
Atmosphère :Corr/Gamme m. : 000/5000 µV
Instrument : NETZSCH DSC 200F3 240-20-0098-L Fichier : C:\NETZSCH\Proteus6\data\gerald\PEG-N3.ngb-sd5 Remarque : in pierced Al pan, to 300°C at 10K/min
10.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 100.0Température /°C
-5
-4
-3
-2
-1
0
DSC /(mW/mg)
Principal 2015-05-12 17:00 Utilisateur: Utilisateur DSC
21.5 °C21.9 °C21.7 °C0.208 J/(g*K)
Transition vitreuse: Onset:Milieu:Inflexion:Delta Cp*:
-144.6 J/g53.8 °C
Pic complexe: Aire:Pic:
[1.5]
↑ exo
Figure S8. DSC thermogram for PEG-‐azide 2.
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Figure S9. Cryo-‐TEM image of PEG2000-‐b-‐PFPE1200-‐b-‐PEG2000 triblock copolymer in aqueous solution at a concentration of 50 mg mL-‐1.
Figure S10. Plots of fluorescence vibronic intensities ratio (I3/I1) as a function of the triblock copolymer concentration as measured from emission spectra.