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1 Supporting Information for:

2 Water/Cosolvent Attraction Induced Phase Separation: a

3 Molecular Picture of Cononsolvency

4 Taisen Zuo1,2, Changli Ma1,2, Guisheng Jiao1,2, Zehua Han1,2,3, Shiyan Xiao4, Haojun
5 Liang4, Liang Hong5, Daniel Bowron6,*, Alan Soper6, *, Charles C. Han7, He Cheng1,2, *

1
6 China Spallation Neutron Source (CSNS), Institute of High Energy Physics (IHEP),
7 Chinese Academy of Science(CAS), Dongguan 523803, China

2
8 Dongguan Institute of Neutron Science (DINS), Dongguan 523808, China

3
9 University of Chinese Academy of Sciences, Beijing 100049, China

4
10 CAS Key Laboratory of Soft Matter Chemistry, Collaborative Innovation Center of
11 Chemistry for Energy Materials, Department of Polymer Science and Engineering,
12 University of Science and Technology of China, Hefei, Anhui 230026, China.

5
13 School of Physics and Astronomy &Institute of Natural Sciences, Shanghai Jiao Tong
14 University, Shanghai 200240, China

6
15 ISIS Facility, Rutherford Appleton Laboratory, Harwell Science and Innovation Campus,
16 Didcot OX11 0QX, United Kingdom

7
17 Institute for Advanced Study, Shenzhen University, Shenzhen, 508060, China

18 The corresponding authors:

19 Daniel Bowron, Email: daniel.bowron@stfc.ac.uk

20 Alan Soper, Email: alan.soper@stfc.ac.uk

21 He Cheng, Email: chenghe@ihep.ac.cn

22 Tel: +86-769-8915-6445; Fax: +86-769-8915-6441.

23
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24

25 Fourier Transforms of MD simulations. Neutron total scattering profiles of PDEA in

26 fully deuterated water and ethanol as shown in Figure 1b and Figure S1 were compared

27 with the Fourier Transforms of molecular dynamics simulations. The sizes of the

28 simulation boxes are about 170 Å . According to the Periodic Boundary Conditions

29 (PBCs), the smallest accessible scattering vector is about 2/170 = 0.04 Å-1 . Scattering

30 profiles with scattering vector lower than 0.04 Å-1 must be calculated without the PBCs.

31 To keep us in a safe condition, all of the scattering curves with scattering vector from

32 0.06 Å-1 to 50 Å-1 (we call it diffraction curves) were calculated by the Debyer software

33 package1 with the PBCs, while the scattering curves with scattering vector from 0.02 Å-1

34 to 1 Å-1 (small angle scattering of PDEA in fully deuterated water) were fitted by the

35 “gmx sans” tool (direct Fourier Transform software) of GROMACS without PBCs. The

36 small angle scattering curves were shifted to overlap with the diffraction analysed results

37 in the scattering vector ranging from 0.06 Å-1 to 1 Å-1 . The resultant curves were then

38 plotted with the experimental data as shown in Figure 1b and Figure S1. As for the half

39 deuterated and fully protonated samples, only the diffraction curves calculated by the

40 Debyer software package were fitted to the scattering curves. The Fourier Transforms of

41 the samples with hydrogenous solvent are not so good at low Q due to the nonlinear

42 inelastic scattering background from the hydrogen atoms which cannot be efficiently

43 subtracted theoretically2.
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5 5
Fully protonated FH

F(Q) (barn/Sr/atom)
Fully protonated FH
(a) (b)
F(Q) (barn/Sr/atom)
Half deuterated HD Half deuterated HD
4 4 Fully deuterated FD
Fully deuterated FD
FH Simulation FH Simulation
Ethanol 3 HD Simulation Ethanol
3 HD Simulation
FD Simulation 4.1 mol% FD Simulation 8.7 mol%
2 2

1 1

0 0
0.1 1 10 0.1 1 10
-1 -1
44 Q (Å ) Q (Å )

Fully protonated FH Fully protonated FH

F(Q) (barn/Sr/atom)
F(Q) (barn/Sr/atom)

5 (c) 5 (d)
Half deuterated HD Half deuterated HD
Fully deuterated FD Fully deuterated FD
4 FH Simulation 4 FH Simulation
HD Simulation Ethanol HD Simulation Ethanol
3 FD Simulation 14.2 mol% 3 FD Simulation 60.5 mol%

2 2

1 1

0 0
0.1 1 10 0.1 1 10
-1 -1
45 Q (Å ) Q (Å )

46 Figure S1. Neutron total scattering profiles and the Fourier Transforms from molecular dynamic

47 simulations. (a), (b), (c) and (d) are the neutron total scattering profiles of PDEA water ethanol

48 solutions at 4.1 mol%, 8.7 mol%, 14.2 mol% and 60.5 mol% ethanol concentrations at 20 ℃, with

49 water and ethanol molecules fully deuterated (FD), half deuterated (HD) and fully protonated (FH).

50 The curves of FD and HD samples were shifted upward 2 and 1 barn/Sr/atom for clarity.

51
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52 SANS data fitting.

PDEA in PDEA in
Macro Cross Section (cm )

Macro Cross Section (cm )

-1

-1
C2D5OD(4.1 mol% ) / D2O C2D5OD (8.7 mol%) / D2O
(a) Data (b) Data
PolymerExclVol fit PolymerExcelVol fit
0.1 Rg = 32.2 0.1 Rg = 31.8
1/ = 2.0 1/ = 2.0

0.1 1 0.1 1
-1 -1
53 Q (Å ) Q (Å )
Macro Cross Section (cm )

Macro Cross Section (cm )

PDEA in
-1

-1
C2D5OD (14.2 mol%) / D2O PDEA in
C2D5OD (60.5 mol%) / D2O
Data
(c) Data
PolymerExclVol fit
(d) PolymerExclVol fit

0.1 Rg = 32.9
0.1 Rg = 36.8
1/ = 2.0
1/ = 1.67

0.1 1 0.1 1
-1 -1
54 Q (Å ) Q (Å )

55 Figure S2. Radius of gyration of PDEA fitted from the small angle neutron scattering (SANS) curves.

56 The small angle scattering of PDEA in fully deuterated water-ethanol solution in Figure S1 were

Σ
57 exported by the data reduction software Gudrun with absolute intensity of macro cross section
Ω

58 (cm-1). (a), (b), (c) and (d) are the best fits of the exported small angle scattering data of the PDEA in

59 fully deuterated water ethanol solution at ethanol molar concentrations of 4.1 mol%, 8.7 mol%,

60 14.2 mol% and 60.5 mol%, respectively.

61

62 The fitting equation is the Polymer_Excl_Vol formula from the Data Analysis Package

63 of NIST Center for Neutron Research,

Σ
64 = Δρ 2 NVm P(Q) + bkg (1)
Ω
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65 where  is the macromolecule volume fraction, Δρ is the scattering contrast of the

66 macromolecule and the solvent, N is the degree of polymerization and Vm is the volume

67 of a monomer.

68 P(Q) in formula (0) is determined by equation

1 1 1 1
69 P(Q) = γ( , U) - γ( , U) (2)
1
2ν 1
ν
ν*U 2ν
ν*U ν

70 Where

U
71 γ(x, U) = 0
dtexp(-t)t x -1

72

Q 2 R g 2 (2ν + 1)(2ν + 2)
73 U =
6

1
74 Here, is the Porod exponent or factual dimension of the scattering object and is the
ν

75 scaling factor.

76 In ethanol-poor region, PDEA is a Gaussian coil without exclude volume, so =

77 2.0; while in ethanol-rich region, PDEA has excluded volume with ν = 1.67 according to

78 the mean field theory. Therefore, the radius of gyration of PDEA can be fitted, as shown

79 in Figure S2.

80
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81 Scaling of the radius of gyration

6
Degree of Polymerization of PDEA: 5
5 (a) 10 4 (b)
4.55 30 MD Simulations
3
Rg (nm)

4 60 Linear Fit

Rg (nm)
3.19 96 2 N = 121,
3 160 Rg = 3.68 nm
2.41
2 slope = 0.64 + 0.03
1.45 1
1 0.74

0 50 100 150 200 10 100

82 Time (ns) Degree of Polymerization

83 Figure S3. Scaling of the radius of gyration R g of PDEA in the good solvent of ethanol. (a) Evolution

84 of the R g of PDEA with 10, 30, 96 and 160 monomers in pure ethanol. (b) Scaling of R g Vs. the

85 degree of polymerization.

86 According to the scaling law

87 R g  N1/  (3)

88 where, N is the degree of polymerization. The averaged R g s of PDEA with degree of

89 polymerization of 10, 30, 60, 96 and 160 from Figure S3(a) were then fitted with equation

90 (3). The fitted results showed that 1 / ν equals 0.64 ± 0.03. The real degree of

91 polymerization of PDEA was determined to be 121, with R g equals 3.68 nm in a good

92 solvent.

93 The resultant PDEA chains in the simulation box of Figure 1(c) is

94
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95 Figure S4. The conformation of PDEA inside the simulation box of Figure 1(c).
96

3.0 8.7 mol% ethanol with PDEA

F(Q) (barn/Sr/atom)

F(Q) (barn/Sr/atom)
8.7 mol% ethanol with PDEA
8.7 mol% ethanol without PDEA 0.2 8.7 mol% ethanol without PDEA
2.5
2.0
1.5 (a) 0.0

1.0 (b)
0.5 -0.2

0.0
-0.5 -0.4
0.1 1 10 1 10
-1 -1
97 Q (Å ) Q (Å )

98 Figure S5. Structure of water ethanol solution is not perturbed by the presence of PDEA (a) Scattering

99 profiles of 8.7 mol% C2D5OD in D2O with and without 0.1 mol% (monomer concentration) PDEA.

100 (b) Scattering profiles of 8.7 mol% C2H5OH in H2O with and without 0.1 mol% (monomer

101 concentration) PDEA solvated.

102 The low Q part in Figure S5 is the conformation of PDEA macromolecule, and

103 the high Q part corresponds to the most-possible all-atom positions of water-ethanol

104 mixture. Because the black and red curve overlap with each other at high Q region, we

105 concluded that the presence of PDEA macromolecule does not perturb water-ethanl

106 structures.
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5 4.0
(a) 3.5 (b)
4 Ethanol molar ratio: Ethanol molar ratio:
3.0
g (r) OW-HW

g (r) HW-HW
4.1 mol% 4.1 mol%
3 2.5
8.7 mol% 8.7 mol%
14.2 mol% 2.0 14.2 mol%
2 60.5 mol% 1.5 60.5 mol%
1.0
1
0.5
0 0.0
1 2 3 4 5 6 7 8 1 2 3 4 5 6 7 8
107 r (Å) r (Å)

3.0
3.0 Ethanol molar ratio: (c) 2.5 Ethanol molar ratio: (d)
2.5 4.1 mol% 4.1 mol%
8.7 mol% 2.0

g (r) HE-HE
g (r) OE-HE

2.0 8.7 mol%

14.2 mol% 14.2 mol%
1.5 60.5 mol% 1.5
60.5 mol%
1.0 1.0

0.5 0.5

0.0 0.0
1 2 3 4 5 6 7 8 1 2 3 4 5 6 7 8
108 r (Å) r (Å)

109 Figure S6. Local structure of water (W) and ethanol (E). (a) g(r) OW-HW (OW means oxygen atoms of

110 water, HW is the hydrogen atom of water); (b) g(r) HW-HW; (c) g(r) OE-HE, (OE means oxygen atom of

111 ethanol, HE is the hydroxyl hydrogen atom of ethanol); (d) g(r) HE-HE.

112
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113 PDEA ethanol and water interaction energy calculation. All of the interaction of
114 between the two components in the ternary system were calculated by the “rerun” tool of

115 Gromacs simulation package following Dalgicdir et al3, including the interaction energy

116 between water ethanol in Figure 4, Figure 5(a) and the Lennard Jones interaction between

117 PDEA and ethanol plus the electrostatic interaction between PDEA and water ethanol

118 mixture in Figure 6(b). Selected atoms or molecules in the system were forced to follow

119 the previously simulated trajectories and potential energy of the selected atoms were then
120 collected. Potential energy between  and  components U − was calculated by

121 U− = U+ − U − U (4)

122 Where U + means both  and  were selected U  and U means  or  were

123 selected for potential energy calculation. In calculating the Lennard Jones energy between

124 PDEA and ethanol in Figure 6(b), all the atoms of PDEA and ethanol were selected for

125 the interaction energy calculation except the carbonyl group of PDEA and the hydroxyl

126 group of ethanol.

127 Table S1: Molar fraction and molecular numbers of PDEA water and ethanol in the MD

128 simulations.

Molar fraction Molar fraction Molar fraction

No. ethanol No. water
of PDEA of ethanol of water

0.10% 4.10% 95.80% 5212 121979

0.10% 8.70% 91.20% 10478 109451

0.10% 14.20% 85.70% 15644 94787

0.17% 60.53% 39.30% 42917 27853

129

130
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131 Table S2: Number of ethanol and water molecules in the MD simulations in calculating

132 the excess enthalpy of mixing ethanol and water without PDEA in Figure 4(a). Density

133 of the water ethanol mixture were also shown.

Molar fraction
No. ethanol No. water Density
of ethanol

4.1% 5212 121979 0.983

8.7% 10478 109451 0.970

14.2% 15644 94787 0.955

27.4% 33720 89400 0.920

60.6% 42917 27853 0.857

134

135

136
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137 References:
138 (1) https://debyer.readthedocs.io/en/latest/.
139 (2) Soper, A. K. Inelasticity corrections for time-of-flight and fixed wavelength neutron
140 diffraction experiments. Molecular Physics 2009, 107, 1667-1684.
141 (3) Dalgicdir, C.; Rodrí guez-Ropero, F.; van der Vegt, N. F. A. Computational
142 calorimetry of PNIPAM cononsolvency in water/methanol mixtures. J. Phys. Chem.
143 B 2017, 121, 7741-7748.
144

145