the royal society of chemistry · 2014. 8. 27. · 1 supplementary information thermodynamic and...
TRANSCRIPT
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Supplementary information
Thermodynamic and kinetic properties of interpolymer complexes assessed by Isothermal Titration Calorimetry and Surface Plasmon Resonance
Samuel C. Bizley,a Adrian C. Williams a and Vitaliy V. Khutoryanskiy a
aReading School of Pharmacy, University of Reading, Whiteknights, PO Box 224,
Reading, Berkshire, RG6 6AD, UK. E-mail: [email protected]; Tel: +44
(0) 118 373 6119
Thermodynamic considerations
∆𝐺𝑀 = ∆𝐻𝑀 - 𝑇∆𝑆𝑀
Spontaneous formation of polymer-polymer complexes in solutions requires Gibbs
free energy ( ) to be negative; this requires the enthalpy of a reaction ( ) to be ∆𝐺𝑀 ∆𝐻𝑀
negative or entropy ( ) to be large and positive. 1,2∆𝑆𝑀
The change in enthalpy measured by the ITC H observed) is the sum of 3 terms:(∆
∆𝐻 𝑜𝑏𝑠𝑒𝑟𝑣𝑒𝑑 = ∆𝐻 𝑏𝑖𝑛𝑑𝑖𝑛𝑔 + ∆𝐻 𝑖𝑜𝑛𝑖𝑧𝑎𝑡𝑖𝑜𝑛 + ∆𝐻 𝑐𝑜𝑛𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛
Electronic Supplementary Material (ESI) for Soft Matter.This journal is © The Royal Society of Chemistry 2014
mailto:[email protected]
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Injection start
Association period Rmax Stop injection
Dissociation period
Figure S1. Example Biacore sensorgram, detailing ka determination. Association rate (ka)
was calculated via BIAevaluation software. Software fits data to a standard local kinetics
model obtained using injection start, association period, Rmax and polymer concentration
values. Data was transformed producing ka (see Table 2) as a measure of time and molar
concentration (M-1s-1).
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-0.30
-0.25
-0.20
-0.15
-0.10
-0.05
0.00
0.05
0 500 1000 1500 2000 2500
µcal
/sec
Time, s-0.30
-0.25
-0.20
-0.15
-0.10
-0.05
0.00
0.05
0 500 1000 1500 2000 2500
µcal
/sec
Time, s
-0.30
-0.25
-0.20
-0.15
-0.10
-0.05
0.00
0.05
0 500 1000 1500 2000 2500
µcal
/sec
Time, s -0.30
-0.25
-0.20
-0.15
-0.10
-0.05
0.00
0.05
0 500 1000 1500 2000 2500µc
al/s
ec
Time, s
A B
C D
Figure S2. Isothermal titration calorimetry isotherms obtained by titrating (A) water, (B) 0.2
% w/v PAA, (C) 0.2 % w/v PMAA and (D) 0.2 % w/v TA with water at pH 2.0.
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-0.3
-0.25
-0.2
-0.15
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-0.05
0
0.05
0 500 1000 1500 2000 2500
µcal
/sec
Time, s-0.3
-0.25
-0.2
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-0.05
0
0.05
0 500 1000 1500 2000 2500
µcal
/sec
Time, s
-0.3
-0.25
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-0.15
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-0.05
0
0.05
0 500 1000 1500 2000 2500
µcal
/sec
Time, s-0.3
-0.25
-0.2
-0.15
-0.1
-0.05
0
0.05
0 500 1000 1500 2000 2500
µcal
/sec
Time, s
-0.3
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-0.2
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-0.1
-0.05
0
0.05
0 500 1000 1500 2000 2500
µcal
/sec
Time, s-0.3
-0.25
-0.2
-0.15
-0.1
-0.05
0
0.05
0 500 1000 1500 2000 2500
µcal
/sec
Time, s
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-0.05
0
0.05
0 500 1000 1500 2000 2500
µcal
/sec
Time, s-0.30
-0.25
-0.20
-0.15
-0.10
-0.05
0.00
0.05
0 500 1000 1500 2000 2500
µcal
/sec
Time, s
A B
C D
E F
G H
Figure S3. Isothermal titration calorimetry isotherms obtained by titrating (A) 0.2 % w/v
DEX, (B) 0.2 % w/v HEC, (C) 0.2 % w/v MC, (D) 0.2 % w/v PAM, (E) 0.2 % w/v PEO, (F)
0.2 % w/v PVA, (G) 0.2% w/v PMVE and (H) 0.2 % w/v PVP with water at pH 2.0.
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-2
3
8
13
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0 1000 2000
μcal
/sec
Time, s
-2
3
8
13
18
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0 1000 2000
μcal
/sec
Time, s
-2
3
8
13
18
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0 1000 2000
μcal
/sec
Time, s
-2
3
8
13
18
23
0 1000 2000μc
al/s
ecTime, sec
-15
-10
-5
0
5
10
0 1000 2000
μcal
/sec
Time, s
A B
C D
E
Figure S4. Isothermal titration calorimetry isotherms obtained by titrating (A) 0.2 % w/v
HEC, (B) 0.2 % w/v PEO, (C) 0.2 % w/v PVA, (D) 0.2 % w/v PMVE and (E) 0.2 % w/v
PVP with 2 % w/v poly (acrylic acid) solutions at pH 2.0.
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-23
-18
-13
-8
-3
2
0 1000 2000μc
al/s
ec
Time, s-2
3
8
13
18
23
0 1000 2000
μcal
/sec
Time, s
-23
-18
-13
-8
-3
2
0 1000 2000
μcal
/sec
Time, s-2
3
8
13
18
23
0 1000 2000μc
al/s
ec
Time, s
-2
3
8
13
18
23
0 1000 2000
μcal
/sec
Time, s
-2
3
8
13
18
23
0 1000 2000
μcal
/sec
Time, s
-2
3
8
13
18
23
0 1000 2000
μcal
/sec
Time,s
A
B
C
D
E F
G
Figure S5. Isothermal titration calorimetry isotherms obtained by titrating (A) 0.2 % w/v
DEX, (B) 0.2 % w/v HEC, (C) 0.2 % w/v PAM, (D) 0.2 % w/v PEO, (E) 0.2 % w/v PVA,
(F) 0.2 % w/v PMVE and (G) 0.2% w/v PVP with 2 % w/v poly (methacrylic acid)
solutions at pH 2.0.
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-23
-18
-13
-8
-3
2
0 1000 2000μc
al, s
ec
Time, s-2
3
8
13
18
23
0 1000 2000
μcal
, sec
Time, s
-32
-22
-12
-20 1000 2000
μcal
/sec
Time, s -30-20-10
0102030
0 1000 2000μcal
/sec
Time, s
-23
-18
-13
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-3
2
0 1000 2000
μcal
/sec
Time, s-2
3
8
13
18
23
0 1000 2000
μcal
/sec
Time, s
-23
-18
-13
-8
-3
2
0 1000 2000
μcal
/sec
Time, s
-2
3
8
13
18
23
0 1000 2000
μcal
/sec
Time, s
A
B
C
D
E
F
G
H
Figure S6. Isothermal titration calorimetry isotherms obtained by titrating (A) 0.2 % w/v
HEC, (B) 0.2 % w/v MC, (C) 0.2 % w/v PAM, (D) 0.2 % w/v PEO, (E) 0.2 % w/v PVA, (F)
0.2 % w/v PMVE, (G) 0.2% w/v PVP and (H) 0.2 % w/v DEX with 2 % w/v tannic acid
solutions at pH 2.0.
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PAA HEC
Figure S7. Turbidity of polymer combinations, 0.2 % w/v acidic compound (1.5 mL) was
mixed with 0.2 % w/v non-ionic polymer (1.5 mL) at pH 2.0 and stirred for 1 minute.
0
10000
20000
30000
40000
0 1000 2000 3000 4000
Biac
ore
resp
onse
, RU
Time, s
TA
PAA
PMAA
-1500
8500
18500
28500
38500
0 1000 2000 3000 4000
Biac
ore
resp
onse
, RU
Time, s
TA
PAA
PMAA
0
10000
20000
30000
40000
0 1000 2000 3000 4000
Biac
ore
resp
onse
, RU
Time, s
TA
PAA
PMAA
0
10000
20000
30000
40000
0 1000 2000 3000 4000
Biac
ore
resp
onse
, RU
Time, s
TA
PAA
PMAA
0
10000
20000
30000
40000
0 1000 2000 3000 4000
Biac
ore
resp
onse
, RU
Time, s
TA
PAA
PMAA
A B
C D
E
Figure S8. Biacore sensorgrams for the formation of IPCs between acidic compounds and
(A) PEO, (B) HEC, (C) PVP, (D) PMVE and (E) PVA. Concentrations are 0.2% w/v for
acidic compounds and 0.2% w/v for non-ionic polymer solutions at pH 2.0.
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References
1 Ababou and E. J. Ladbury, Journal of Molecular recognition. 2007, 21, 4.2 M. J. Blandamer, P. M. Cullis and J. B. F. N. Engberts, Journal of the Chemical
Society-Faraday Transactions. 1998, 94, 2261.