Polymers 2017, 9, 50; doi:10.3390/polym9020050
S1 of S6
Supplementary Materials: The Effect of Molar Mass
and Charge Density on the Formation of Complexes
between Oppositely Charged Polyelectrolytes
Feriel Meriem Lounis, Joseph Chamieh, Laurent Leclercq, Philippe Gonzalez and Hervé Cottet
1. Preparation of the PEC Mixtures
The concentrations of the oppositely charged polyelectrolytes for the preparation of PLL-PAMAMPS
mixtures as well as the investigated ionic strengths are summarized in Tables S1 and S2.
Table S1. Concentrations of oppositely charged polyelectrolytes solutions for the preparation of
PLL-PAMAMPS 100% mixtures.
DP+
I (M)
[PAMAMPS] Stock
Solution (g/L) (*)
[PLL] Stock
Solution (g/L) (*)
1.14
5
1.68
250
1.79
1.89
1.34
100
1.63
1.73
50
1.1
1.2
1.3
1.4
0.85
1.99
20
1.13
1.27
[PLL] Diluted
Solutions (g/L) (*)
2.5; 2; 1.5; 1.25; 1;
0.8; 0.6; 0.5; 0.4; 0.3; 0.2
2.5; 2; 1.5; 1.25; 1;
0.8; 0.6; 0.5; 0.4; 0.3; 0.2
2.5; 2; 1.5; 1.25; 1;
0.8; 0.6; 0.5; 0.4; 0.3; 0.2
2.5; 2; 1.5; 1.25; 1;
0.8; 0.6; 0.5; 0.4; 0.3
2.5; 2; 1.5; 1.25; 1;
0.8; 0.6; 0.5; 0.4; 0.3; 0.2
2.5;2; 1.5;1.25; 1;
0.8; 0.6; 0.5; 0.4; 0.3; 0.2; 0.1
3; 2.5; 2; 1.6; 1.2; 1; 0.8; 0.6
3; 2; 1.6; 1.2; 0.8; 0.7; 0.6; 0.5; 0.4
2; 1.6; 1.2; 0.8; 0.7; 0.5
4; 3; 2; 1.6; 1.2; 1; 0.8
2.5; 2; 1.5; 1.25; 1;
0.8; 0.6; 0.5; 0.4; 0.3; 0.2
2.5; 2; 1.5;1.25; 1;
0.8; 0.6;0.5; 0.4; 0.3;0.2; 0.1
2.5; 2;1.5; 1.25; 1;
0.8;0.6; 0.5; 0.4;0.3; 0.2; 0.1
1.5; 1.25; 1: 0.8; 0.6;
0.5; 0.4; 0.3; 0.2; 0.1
VPAMAMPS
(µL) (a)
VPLL
(µL) (b)
Vf (µL) (c)
100
100
200
(*) For each FACCE experiment, PAMAMPS and PLL stock solutions as well as PLL diluted solutions were
prepared in the same Tris-HCl-NaCl buffer pH 7.4 (12 mM Tris, 10 mM HCl and appropriate amount of NaCl to
adjust the ionic strength of the medium);
PLL diluted solutions in the mixtures;
(c)
(a)
Volume of PAMAMPS stock solution in the mixtures;
(b)
Volume of
final volume of the mixtures.
Table S2. Concentrations of oppositely charged polyelectrolytes solutions for the preparation of
PLL-PAMAMPS 15% mixtures.
DP+
I (M)
[PAMAMPS] Stock
Solution (g/L) (*)
[PLL] Stock
Solution (g/L) (*)
3.2
5
0.3
250
0.32
0.39
0.245
0.263
100
0.28
0.315
[PLL] Diluted
Solutions (g/L) (*)
2.5; 2; 1.5; 1.25; 1; 0.8; 0.6
2.5; 2; 1.5; 1.25; 1;
0.8; 0.6; 0.5; 0.4; 0.3
2.5; 2; 1.5; 1.25; 1;
0.8; 0.6; 0.5; 0.4; 0.3
2.5; 2; 1.5; 1; 0.8;
0.6; 0.5; 0.4; 0.3
2.5; 2; 1.5; 1.25; 1:
0.8; 0.6; 0.5; 0.4; 0.3
2.5; 2; 1.5; 1.25; 1;
0.8; 0.6; 0.5; 0.4; 0.3; 0.2
2.5; 2; 1.5; 1.25; 1;
0.8; 0.6; 0.5; 0.4; 0.3; 0.2
VPAMAMPS (µL) (a)
VPLL (µL) (b)
Vf (µL) (c)
100
100
200
Polymers 2017, 9, 50; doi:10.3390/polym9020050
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0.2
4; 3; 2.5; 2; 1.6; 1.2; 1; 0.8
3; 2.5; 2; 1.6; 1.2;
1; 0.8; 0.6; 0.4
3; 2.5; 2; 1.6; 1.2;
1; 0.8; 0.6; 0.4
4; 3; 2.5; 2; 1.6; 1.2; 1;
0.8; 0.6; 0.4; 0.2
2.5; 2; 1.5; 1.25; 1;
0.8; 0.6; 0.5; 0.4; 0.3; 0.2
2.5; 2; 1.5; 1.25; 1;
0.8; 0.6; 0.5; 0.4; 0.3; 0.2
2.5; 2; 1.5; 1.25; 1;
0.8; 0.6; 0.5; 0.4; 0.3; 0.2
2.5; 2; 1.5; 1.25; 1;
0.8; 0.6; 0.5; 0.4; 0.3; 0.2
0.234
50
0.267
0.301
0.1
0.12
20
0.13
0.15
(*) For each FACCE experiment, PAMAMPS and PLL stock solutions as well as PLL diluted solutions were
prepared in the same Tris-HCl-NaCl buffer pH 7.4 (12 mM Tris, 10 mM HCl and appropriate amount of NaCl to
adjust the ionic strength of the medium).
(a)
Volume of PAMAMPS stock solution in the mixtures;
(b)
Volume of
PLL diluted solutions in the mixtures; (c) final volume of the mixtures.
2. Isotherms of Adsorption
The influence of the ionic strength and the chemical charge density on the thermodynamic
parameters on the interactions between PLL and PAMAMPS was studied by plotting 29 isotherms of
adsorption displayed in Figures S1–S8 with the non-linear curve fitting allowing the determination
of the binding site constants and the chain stoichiometries.
20
18
16
14
ń
12
10
8
6
1.68 M
4
1.79 M
2
1.89 M
0
0
0.02
0.04
0.06
[PLL] (mM)
Figure S1. Isotherms of adsorption and non-linear curve fitting obtained for the interactions between
PLL250 and PAMAMPS 100% at different ionic strengths as noticed on the graph. Experimental
conditions: PDADMAC coated capillary 33.5 cm (8.5 cm to the detector) × 50 µm i.d. Background
electrolyte: 12 mM Tris, 10 mM HCl and appropriate amount of NaCl, pH 7.4. Applied voltage: +1 kV
with a co-hydrodynamic pressure of +5 mbar. Detection at 200 nm. Samples were prepared in the
background electrolyte by 50/50 v/v dilution of PAMAMPS and PLL solutions according to Table S1.
Polymers 2017, 9, 50; doi:10.3390/polym9020050
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60
50
ǹ
40
30
20
1.344 M
1.623 M
10
1.728 M
0
0
0.05
0.1
0.15
[PLL] (mM)
Figure S2. Isotherms of adsorption and non-linear curve fitting obtained for the interactions between
PLL100 and PAMAMPS 100% at different ionic strengths as noticed on the graph. Experimental
conditions were the same as in Figure S1.
120
A
100
ṅ
80
60
1100mM
40
1200mM
1300mM
20
1400mM
0
0
0.1
0.2
0.3
[PLL] (mM)
Figure S3. Isotherms of adsorption and non-linear curve fitting obtained for the interactions between
PLL50 and PAMAMPS 100% at different ionic strengths as noticed on the graph. Experimental
conditions were the same as in Figure S1.
Polymers 2017, 9, 50; doi:10.3390/polym9020050
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300
250
ǹ
200
150
0.85 M
100
0.99 M
1.13 M
50
1.27 M
0
0
0.2
0.4
0.6
0.8
1
[PLL] (mM)
Figure S4. Isotherms of adsorption and non-linear curve fitting obtained for the interactions between
PLL20 and PAMAMPS 100% at different ionic strengths as noticed on the graph. Experimental
conditions were the same as in Figure S1.
6
5
4
ǹ
3
2
0.3 M
0.35 M
1
0.39 M
0
0
0.01
0.02
0.03
0.04
0.05
[PLL] (mM)
Figure S5. Isotherms of adsorption and non-linear curve fitting obtained for the interactions between
PLL250 and PAMAMPS 15% at different ionic strengths as noticed on the graph. Experimental
conditions were the same as in Figure S1.
Polymers 2017, 9, 50; doi:10.3390/polym9020050
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14
12
10
ǹ
8
6
0.245 M
0.263 M
4
0.28 M
2
0.315 M
0
0
0.02
0.04
0.06
0.08
0.1
0.12
[PLL] (mM)
Figure S6. Isotherms of adsorption and non-linear curve fitting obtained for the interactions between
PLL100 and PAMAMPS 15% at different ionic strengths as noticed on the graph. Experimental
conditions were the same as in Figure S1.
30
PLL50 VS PAMAMPS15%
25
ṅ
20
15
200mM
10
234mM
5
267mM
301mM
0
0
0.1
0.2
0.3
[PLL] (mM)
Figure S7. Isotherms of adsorption and non-linear curve fitting obtained for the interactions between
PLL50 and PAMAMPS 15% at different ionic strengths as noticed on the graph. Experimental
conditions were the same as in Figure S1.
Polymers 2017, 9, 50; doi:10.3390/polym9020050
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60
50
40
ǹ
30
0.1 M
20
0.12 M
0.13 M
10
0.15 M
0
0
0.2
0.4
0.6
[PLL] (mM)
Figure S8. Isotherms of adsorption and non-linear curve fitting obtained for the interactions between
PLL20 and PAMAMPS 15% at different ionic strengths as noticed on the graph. Experimental
conditions were the same as in Figure S1.