Supporting Information
Complexation of Dodecyl-Substituted Poly(acrylate) by Linked β-Cyclodextrin
Dimers and Trimers in Aqueous Solution
Duc-Truc Pham,a Hanh-Trang Nguyen,a Stephen F. Lincoln,a Jie Wang,b Xuhong Guo,a
Christopher J. Eastonc and Robert K Prud’hommed
a
Department of Chemistry, University of Adelaide, Adelaide, SA 5005, Australia
State Key Laboratory of Chemical Engineering, East China University of Science and
Technology, Shanghai, 200237, China
c
Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia.
d
Department of Chemical Engineering, Princeton University, Princeton, NJ 08544, USA
b
Correspondence to: S. F. Lincoln (E-mail: Stephen.lincoln@adelaide.edu.au)
Contents
2D NOESY 1H NMR Spectrum ...................................................................................................... 2
Isothermal Calorimetric Titration (ITC) Data ................................................................................. 3
Rheological Data
6
1
2D NOESY 1H NMR Spectrum
Figure S1. 2D NOESY 1H NMR (600 MHz) spectrum (mixing time 300 ms) of a solution 1.0 ×
10-3 mol dm-3 in -CDen3bz and 1.0 wt.% in 3% substituted PAAC12 such that the dodecyl
groups substituent concentration is 3.0 × 10-3 mol dm-3 in D2O (pD 7.0 phosphate buffer, I = 0.10
mol dm-3) at 298.2K. Rectangles A and B enclose the cross-peaks arising from interaction
between the β-CD H2-H6 protons of -CD3bz and the PAAC12 C12 2-11 methylene and methyl
protons, respectively. A schematic representation of the complexation between -CD3bz and
PAAC12 is shown above the spectrum.
2
Isothermal Calorimetric Titration (ITC) Data
Figure S2. (a) ITC data for titration of β-CD2ur (3.27 × 10-3 mol dm-3) into 0.2 wt% PAAC12
([C12] = 6.10 × 10-4 mol dm-3) both in aqueous phosphate buffer at pH 7.0 (I = 0.10 mol dm-3) at
298.2 K. The top section shows the heat evolution with time as the titration proceeds. The
bottom section shows the heat evolved with the addition of each aliquot of β-CD2ur solution. The
solid curve represents the best fit of an algorithm for the initial 1:1 β-CD2ur.C12 complexation
which is followed by a rapid second C12 complexation. (b) Speciation plot showing the variation
of the percentages of free and complexed C12 as [β-CD2ur]total/[C12]total increases during the
titration, where the dominant stoichiometry of the complex formed is β-CD2ur.C122.
3
Figure S3. (a) ITC data for titration of β-CD2su (3.19 × 10-3 mol dm-3) into 0.2 wt% PAAC12
([C12] = 6.10 × 10-4 mol dm-3) both in aqueous phosphate buffer at pH 7.0 (I = 0.10 mol dm-3) at
298.2 K. The top section shows the heat evolution with time as the titration proceeds. The
bottom section shows the heat evolved with the addition of each aliquot of β-CD2su solution.
The solid curve represents the best fit of an algorithm for the initial 1:1 β-CD2su.C12
complexation which is followed by a rapid second C12 complexation. (b) Speciation plot
showing the variation of the percentages of free and complexed C12 as [β-CD2su]total/[C12]total
increases during the titration, where the dominant stoichiometry of the complex formed is
β-CD2su.C122.
4
Figure S4. a) ITC data for titration of β-CDen3bz (2.03 × 10-3 mol dm-3) into 0.2 wt% PAAC12
([C12] = 6.10 × 10-4 mol dm-3) both in aqueous phosphate buffer at pH 7.0 (I = 0.10 mol dm-3) at
298.2 K. The top section shows the raw ITC data set where (i) is the data for dilution of
β-CDen3bz and by titration into the buffer solution alone and (ii) is the titration of β-CDen3bz
into 0.2 wt% PAAC12 solution. The bottom section shows the heat evolved with the addition of
each aliquot of β-CDen3bz solution. The solid curve represents the best fit of an algorithm for the
initial 1:1 β-CDen3bz.C12 complexation which is followed by rapid successive second and third
C12 complexations. (b) Speciation plot showing the variation of the percentages of free and
complexed C12 as [β-CDen3bz]total/[C12]total increases during the titration, where the dominant
stoichiometry of the complex formed is β-CDen3bz.C123.
5
Rheological Data
Viscosity /Pa s
1.00
-CD3bz + PAAC12
-CDen3bz + PAAC12
0.10
0.01
0.001
0.01
0.1
1
10
Shear Rate /s-1
100
1000
Figure S5. Viscosity variations with shear rate of 3.3 wt% aqueous solutions of PAAC12 with
-CD3bz and -CDen3bz at pH = 7.0 and [NaCl] = 0.10 mol dm-3 at 298.2 K. The concentration
of the C12 substituents of PAAC12 and those of the -CD groups of β-CD3bz and β-CDen3bz
were equal at 1.01 × 10-2 mol dm-3.
6