Document [original]

Supporting Information

Modifying the Properties of Microemulsion Droplets

by Addition of Thermoresponsive BAB*

Copolymers

Albert Prausea,*, Michelle Hechenbichlerb, Robert F. Schmidta, Sylvain Prévostd, Leide P.

Cavalcantie, André Laschewskyb,c,* and Michael Gradzielskia,*

a Technische Universität Berlin, FG Physical Chemistry/ Molecular Material Science, Straße des

17. Juni 135, 10623 Berlin, Germany

b Department of Chemistry, Universität Potsdam, Karl-Liebknecht-Straße 24–25, 14476,

Potsdam, Germany

c Fraunhofer Institute of Applied Polymer Research IAP, Geiselbergstraße 69, 14476 Potsdam,

Germany

d Institut Laue–Langevin, DS/ LSS, 71 Avenue des Martyrs, CS 20 156, F-38042 Grenoble

Cedex 9, France

e ISIS Facility, STFC, Rutherford Appleton Laboratory, Harwell Campus, Didcot OX11 0QX,

PHYSICAL PROPERTIES

Table S1. Overview of microemulsion components with Mn as the molecular weight, Vsp as the

partial specific volume, Vn as the molecular volume, and 𝑆𝐿𝐷 as the scattering length density.

Building block

Chemical structure

Mn /

g mol-1

Vsp /

cm3 g-1

Vn / nm3

𝑺𝑳𝑫 /

10-4 nm-2

D2O

20.03

0.903

0.0300

6.38

Tween20 (surf)

1227.7

0.913

1.8618

0.768

Tween20 (head)

1071.4

0.846

1.4847

1.067

Tween20 (tail)

156.31

1.351

0.3772

-0.475

EHG (co)

204.31

1.040

0.3527

0.606

IPP (oil)

298.51

1.173

0.5815

-0.073

n-decane (oil)

142.29

1.369

0.3237

-0.489

R1-group (BAB*)

302.48

1 (a)

0.5023

0.771

R2-group (B2AB*)

470.81

1 (a)

0.7818

0.236

R3-group (B(AB*)2)

317.52

1 (a)

0.5273

0.648

Table S2. Overview of synthesized polymers with degree of polymerization (DPnNMR), as obtained

by NMR, of the pDMAm block and the corresponding TR block, the resulting molar mass (Mn),

obtained by NMR, SEC, or UV-vis. The degree of polymerization (DPntheo) refers to the

theoretically calculated number with respect to the determined yield (a). Data were taken from

Reference Prause et al. (2022)1, where additional information is provided.

Architecture

type

Polymers

DPn

Mn / kg mol-1

Ɖ (d)

theo

(a)

NMR

(b)

theo

(a)

NMR

(b)

SEC

(c)

UV-vis

(e)

C12DMAm168

168

213

17.1

1.25

B2A

(C12)2DMAm158

158

193

16.4

1.14

BA2

C12(DMAm172)2

172

(f)

181 (f)

35.0

1.15

BAB*-1

C12DMAm127NPAm31

31 (g)

45 (g)

16.6

1.25

B2AB*-1

(C12)2DMAm158NPAm32

32 (g)

20.4

23.5

1.11

B(AB*-1)2

C12(DMAm172NPAm49)2

(f,g)

51 (f,g)

46.1

1.26

BAB*-2

C12DMAm168DEAm27

27 (g)

45 (g)

20.1

1.25

B2AB*-2

(C12)2DMAm158DEAm22

22 (g)

25 (g)

19.2

1.13

B2AB*-2

C12(DMAm172DEAm29)2

(f,g)

29 (f,g)

42.3

1.14

BAB*-3

C12DMAm168NiPAm33

33 (g)

34 (g)

20.8

1.26

B2AB*-3

(C12)2DMAm158NiPAm21

21 (g)

18 (g)

18.7

1.14

B(AB*-3)2

C12(DMAm172NiPAm32)2

(f,g)

32 (f,g)

42.2

1.15

(a) for calculation, monomer conversion was approximated by the determined yield. (b) by end

group analysis via 1H NMR spectroscopy, using the trimethylsilyl signal of the CTA's Z-group. (c)

from SEC: eluent 0.1 wt% LiBr in NMP, using polystyrene standards for calibration. (d) dispersity

Mw/Mn according to SEC data. (e) by end group analysis via UV-spectroscopy in methanol, using

the π-π* transition band at 309 nm of the C=S double bond of the CTA's Z-group. (f) number is

given per arm. (g) numbers refer to DPn of the thermo-responsive block.

Table S3. Overview of block copolymers with Mn as the molecular weight, Vsp as the partial

specific volume, Vn as the molecular volume, and 𝑆𝐿𝐷 as the scattering length density.

Architecture

type

Polymer

Mn /

kg mol-1

Vsp / cm3 g-1

Vn / nm3

𝑺𝑳𝑫 /

10-4 nm-2

C12DMAm168

17.1

0.8507

24.27

1.037

B2A

(C12)2DMAm158

16.4

0.8525

23.16

1.015

BA2

C12(DMAm172)2

35.0

0.8435

48.97

1.050

BAB*-1

C12DMAm127NPAm31

16.6

0.9071

25.04

1.094

B2AB*-1

(C12)2DMAm158NPAm32

20.4

0.8513

28.78

1.045

B(AB*-1)2

C12(DMAm172NPAm49)2

46.1

0.8561

65.47

1.146

BAB*-2

C12DMAm168DEAm27

20.1

0.8499

29.09

0.987

B2AB*-2

(C12)2DMAm158DEAm22

19.2

0.8516

27.09

0.974

B2AB*-2

C12(DMAm172DEAm29)2

42.3

0.8439

59.34

0.994

BAB*-3

C12DMAm168NiPAm33

20.8

0.8588

29.83

1.111

B2AB*-3

(C12)2DMAm158NiPAm21

18.7

0.8581

26.69

1.070

B(AB*-3)2

C12(DMAm172NiPAm32)2

42.2

0.8524

59.75

1.119

Table S4. Overview of ME–polymer mixtures at fixed polymer and microemulsion’s surfactant

concentration of about 22 g L-1 and 50 mM, respectively, with their composition and polymer-to-

ME ratio c(Polymer)/c(ME) at 25 °C and 55 °C.

Polymer

c(ME) / mM

c(Polymer)/c(ME)

cg / g L-1

c / mM

25 °C

55 °C

25 °C

55 °C

ME-1 a

17.5

1.021

0.579

0.369

1.8

2.8

ME-4

22.2

1.294

0.610

0.322

2.1

4.0

B2A

ME-2

22.4

1.370

0.654

0.430

2.1

3.2

ME-4

22.2

1.359

0.611

0.323

2.2

4.2

BA2

ME-3

21.8

0.624

0.603

0.319

1.0

2.0

BAB*-1

ME-2

21.9

1.316

0.649

0.426

2.0

3.1

ME-4

22.3

1.342

0.554

0.302

2.4

4.5

B2AB*-1

ME-2

22.3

1.094

0.649

0.426

1.7

2.6

ME-4

22.1

1.086

0.614

0.324

1.8

3.4

B(AB*-1)2

ME-3

21.8

0.473

0.617

0.326

0.8

1.5

BAB*-2

ME-1 a

18.0

0.871

0.565

0.360

1.5

2.4

ME-4

21.4

1.039

0.616

0.325

1.7

3.2

B2AB*-2

ME-2

22.1

1.153

0.648

0.426

1.8

2.7

ME-4

22.3

1.165

0.614

0.324

1.9

3.6

B(AB*-2)2

ME-3

22.0

0.519

0.606

0.320

0.9

1.6

BAB*-3

ME-1 a

18.1

0.864

0.556

0.360

1.5

2.4

ME-4

21.4

1.021

0.613

0.324

1.7

3.2

B2AB*-3

ME-2

22.3

1.192

0.653

0.429

1.8

2.8

ME-4

22.4

1.193

0.612

0.323

1.9

3.7

B(AB*-3)2

ME-3

21.8

0.516

0.602

0.318

0.9

1.6

a Polymer and microemulsion’s surfactant concentration of about 18 g L-1 and 41 mM,

respectively.

Table S5. Overview of ME–polymer mixtures at varying polymer and microemulsion's surfactant

concentrations of about 4, 9, 18, and 22 g L-1 and 25, 50, 100 mM, respectively, with their

composition and polymer-to-ME ratio c(Polymer)/c(ME) at 25 °C and 55 °C.

Polymer

c(ME) / mM

c(Polymer)/c(ME)

cg / g L-1

c / mM

25 °C

55 °C

25 °C

55 °C

Variation of polymer concentration: ME–BAB* mixtures

ME-1

4.6

0.266

0.581

0.370

0.5

0.7

ME-1

8.7

0.507

0.578

0.368

0.9

1.4

ME-1 a

17.5

1.021

0.579

0.369

1.8

2.8

ME-4 a

22.2

1.294

0.610

0.322

2.1

4.0

BAB*-2

ME-1

4.3

0.210

0.588

0.375

0.4

0.6

ME-1

8.7

0.421

0.572

0.364

0.7

1.2

ME-1 a

18.0

0.871

0.565

0.360

1.5

2.4

ME-4 a

21.4

1.039

0.616

0.325

1.7

3.2

BAB*-3

ME-1

4.1

0.195

0.588

0.375

0.3

0.5

ME-1

8.8

0.420

0.572

0.364

0.7

1.2

ME-1 a

18.1

0.864

0.565

0.360

1.5

2.4

ME-4 a

21.4

1.021

0.613

0.324

1.7

3.2

Variation of microemulsion concentration: ME-2–B2AB* mixtures

B2A

ME-2

22.3

1.365

0.334

0.227

4.1

6.0

ME-2 a

22.4

1.370

0.654

0.430

2.1

3.2

ME-2

22.9

1.397

1.263

0.876

1.1

1.6

B2AB*-1

ME-2

22.3

1.093

0.336

0.229

3.3

4.8

ME-2 a

22.3

1.094

0.649

0.426

1.7

2.6

ME-2

22.9

1.090

1.277

0.885

0.9

1.2

B2AB*-2

ME-2

22.3

1.157

0.335

0.228

3.5

5.1

ME-2 a

22.1

1.153

0.648

0.426

1.8

2.7

ME-2

22.9

1.147

1.281

0.888

0.9

1.3

B2AB*-3

ME-2

22.3

1.200

0.334

0.227

3.6

5.3

ME-2 a

22.3

1.192

0.653

0.429

1.8

2.8

ME-2

22.9

1.195

1.271

0.881

0.9

1.4

a Identical with ME–polymer samples listed in Table S4.

Rheology

Figure S1. (a) Exemplary shear rheology measurements of ME-3. (b) Zero-shear viscosity as a

function of temperature. The dashed black line indicates the viscosity of the solvent D2O.

110

10-3

10-2

10-1

20 30 40 50 60

10-3

10-2

10-1

/ Pa s

g / s-1

ME-3 55°C

45°C

35°C

25°C

(a)

0 / Pa s

temperature / °C

(b)

Figure S2. Shear rheology measurements (only increasing shear rate shown) of the studied ME–

polymer mixtures containing polymers with (a) no TR block, (b) pNPAm, (c) pDEAm, and (d)

pNiPAm as TR block.

10-3

10-2

10-1

110110

10-3

10-2

10-1

/ Pa s

ME-4 + BA (22 g L-1)

25°C 35°C 45°C 55°C

ME-2 + B2A (22 g L-1)

25°C 35°C 45°C 55°C

ME-3 + BA2 (22 g L-1)

25°C 35°C 45°C 55°C

(a) ME-4 + BAB*-1 (22 g L-1)

25°C 35°C 45°C 55°C

(b)

ME-2 + B2AB*-1 (22 g L-1)

25°C 35°C 45°C 55°C

ME-3 + B(AB*-1)2 (22 g L-1)

25°C 35°C 45°C 55°C

g / s-1

ME-4 + BAB*-3 (22 g L-1)

25°C 35°C 45°C 55°C

ME-2 + B2AB*-3 (22 g L-1)

25°C 35°C 45°C 55°C

(d)

ME-3 + B(AB*-3)2 (22 g L-1)

25°C 35°C 45°C 55°C

/ Pa s

g / s-1

ME-4 + BAB*-2 (22 g L-1)

25°C 35°C 45°C 55°C

ME-2 + B2AB*-2 (22 g L-1)

25°C 35°C 45°C 55°C

(c)

ME-3 + B(AB*-2)2 (22 g L-1)

25°C 35°C 45°C 55°C

Figure S3. Zero-shear viscosity as a function of temperature shown for ME–polymer mixtures

containing polymers (a) without TR-block, (b) with pNPAm, (c) with pDEAm, and (d) with

pNiPAm as TR-block. The up- and downwards measurement were averaged. The dashed black

lines indicate the viscosity of the solvent D2O.

10-3

10-2

10-1

20 30 40 50 6020 30 40 50 60

10-3

10-2

10-1

0 / Pa s

ME-4 + BA (22 g L-1)

ME-2 + B2A (22 g L-1)

ME-3 + BA2 (22 g L-1)

(a)

ME-3

ME-4 + BAB*-1 (22 g L-1)

ME-2 + B2AB*-1 (22 g L-1)

ME-3 + B(AB*-1)2 (22 g L-1)

(b)

ME-3

temperature / °C

ME-4 + BAB*-3 (22 g L-1)

ME-2 + B2AB*-3 (22 g L-1)

ME-3 + B(AB*-3)2 (22 g L-1)

(d)

ME-3

0 / Pa s

temperature / °C

ME-4 + BAB*-2 (22 g L-1)

ME-2 + B2AB*-2 (22 g L-1)

ME-3 + B(AB*-2)2 (22 g L-1)

(c)

ME-3

Figure S4. Polymer concentration effects on (a) the zero-shear viscosity of the reference ME–

polymer mixture with the polymer BA, and the normalized viscosities for ME–BAB* mixtures

containing polymers with (b) pDEAm, and (c) pNiPAm as TR-block.

20 30 40 50 60

10-3

10-2

10-1

20 30 40 50 6020 30 40 50 60

ref

0 / Pa s

temperature / °C

ME + BA

ME-1 + 9 g L-1

ME-1 + 18 g L-1

ME-4 + 22 g L-1

(a)

temperature / °C

ME + BAB*-3

ME-1 + 9 g L-1

ME-1 + 18 g L-1

ME-4 + 22 g L-1

(c)

ref

temperature / °C

ME + BAB*-2

ME-1 + 9 g L-1

ME-1 + 18 g L-1

ME-4 + 22 g L-1

(b)

Figure S5. Microemulsion concentration effects on (a) the zero-shear viscosity of the reference

ME–polymer mixture with the polymer B2A, and the normalized viscosities for ME–B2AB*

mixtures containing polymers with (b) pNPAm, (c) pDEAm, and (d) pNiPAm as TR-block

(microemulsion concentrations are given as concentration of the contained surfactant).

10-3

10-2

10-1

20 30 40 50 60

ref

0 / Pa s

ME-2 + B2A (22 g L-1)

25 mM

50 mM

100 mM

(a)

ref

ME-2 + B2AB*-1 (22 g L-1)

50 mM

100 mM

(b)

ref

temperature / °C

ME-2 + B2AB*-3 (22 g L-1)

25 mM

50 mM

100 mM

(d)

ref

temperature / °C

ME-2 + B2AB*-2 (22 g L-1)

25 mM

50 mM

100 mM

(c)

Figure S6. Shear oscillation measurements with the storage modulus (G’) and loss modulus (G”)

at 25 °C and 55 °C of the studied ME–polymer mixtures containing polymers with (a) no TR block,

(b) pNPAm, (c) pDEAm, and (d) pNiPAm as TR block. The measurements were conducted at a

deformation of 2 %.

10-4

10-3

10-2

10-1

100

101

102

10-1 100101102

10-4

10-3

10-2

10-1

100

101

102

G', G'' / Pa

ME-4 + BA (22 g L-1)

, 25°C

, 55°C

ME-2 + B2A (22 g L-1)

, 25°C

, 55°C

(a)

ME-3 + BA2 (22 g L-1)

, 25°C

, 55°C

ME-4 + BAB*-1 (22 g L-1)

, 25°C

, 55°C

ME-2 + B2AB*-1 (22 g L-1)

, 25°C

, 55°C

(b)

ME-3 + B(AB*-1)2 (22 g L-1)

, 25°C

, 55°C

f / Hz

ME-4 + BAB*-3 (22 g L-1)

, 25°C

, 55°C

ME-2 + B2AB*-3 (22 g L-1)

, 25°C

, 55°C

(d)

ME-3 + B(AB*-3)2 (22 g L-1)

, 25°C

, 55°C

G', G'' / Pa

f / Hz

ME-4 + BAB*-2 (22 g L-1)

, 25°C

, 55°C

ME-2 + B2AB*-2 (22 g L-1)

, 25°C

, 55°C

(c)

ME-3 + B(AB*-2)2 (22 g L-1)

, 25°C

, 55°C

LIGHT SCATTERING

Static Light Scattering (SLS)

The mass averaged molecular weight Mw given in Table 1 was determined via I(0) obtained from

the Guinier fit. The mass averaged molecular weight (𝑀w) was estimated via

𝑀w=𝐼(0)

𝑆(0)⋅𝐾⋅𝑐𝑔 (S1)

with 𝐾=4𝜋2𝑛0

𝑁A𝜆4(d𝑛/d𝑐𝑔)2, where K is the optical constant, 𝑐𝑔 the mass concentration of

microemulsion solution, 𝑆(0) the structure factor at 𝑞=0, 𝑛0 the refractive index of the solvent,

d𝑛/d𝑐𝑔 the refractive index increment of the microemulsion, and 𝑁A the Avogadro constant. The

d𝑛/d𝑐𝑔 values of the microemulsions were estimated based on the composition and the refractive

indices of the pure substances.

d𝑛

d𝑐𝑔≈∑𝜙𝑖𝑖 (Δ𝑛

Δ𝑐g)𝑖 with (Δ𝑛

Δ𝑐g)𝑖=𝑛𝑖−𝑛0

𝜌𝑖 (S2)

where 𝜙𝑖 is the volume fraction of the component in the microemulsion droplet, 𝑛𝑖 is the refractive

index of the pure component, i.e., 1.4685 for Tween20, 1.4496 for EHG, and 1.4376 for IPP, and

𝜌𝑖 is the density of the pure component, i.e., 1.095 for Tween20, 0.962 for EHG, and 0.8525 for

IPP. The resulting Δ𝑛/Δ𝑐𝑔 values for Tween20, EHG, and IPP are 0.1283 mL g-1, 0.1264 mL g-1,

and 0.1286 mL g-1, respectively. With this, the d𝑛/d𝑐𝑔 value for the microemulsions ME-1, ME-

3, and ME-4 computes as approximately 0.1281 mL g-1.

The structure factor S(0) was estimated from values obtained from SANS fits at 25 °C and 55 °C.

The structure factor values S(0) for temperatures between 20 and 60 °C were calculated based in

a linear fit of the values at 25 °C and 55 °C obtained from SANS structure factor.

Figure S7. Guinier plot (logarithmically scaled I(q) axis vs. quadratically scaled q axis) of static

light scattering intensities of the microemulsion solutions (a) ME-1, (b) ME-3, and (c) ME-4. Data

of 25, 35, 45, and 55 °C are shown. The solid black lines represent the Guinier fit.

10-2 2×10-2

10-3

10-2

10-1

10-2 2×10-2 10-2 2×10-2

I(q) / cm-1

q / nm-1

ME-1

25°C

35°C

45°C

55°C

(a)

q / nm-1

ME-3

25°C

35°C

45°C

55°C

(b)

q / nm-1

ME-4

25°C

35°C

45°C

55°C

(c)

Figure S8. Guinier plot of static light scattering intensities of ME–polymer complexes of polymers

(a–c) without TR block, (d–f) with pNPAm as TR block, (g–i) with pNiPAm as TR block, and (j–

l) with pDEAm as TR block. The solid black lines represent the Guinier fit.

10-3

10-2

10-1

10-3

10-2

10-1

10-2 2×10-2 10-2 2×10-2

10-2 2×10-2

10-3

10-2

10-1

10-3

10-2

10-1

I(q) / cm-1

ME-4 + C12DMAm168

25°C

35°C

45°C

55°C

(a)

B2A

ME-4 + (C12)2DMAm158

25°C

35°C

45°C

55°C

(b)

pDMAm

BA2

ME-3 + C12(DMAm172)2

25°C

35°C

45°C

55°C

(c)

BAB*-x

I(q) / cm-1

ME-4 + C12DMAm127NPAm27

25°C

35°C

45°C

55°C

(d)

B2AB*-x

ME-4 + (C12)2DMAm158NPAm32

25°C

35°C

45°C

55°C

(e)

x = 1 (pNPAm)

B(AB*-x)2

ME-3 + C12(DMAm172NPAm49)2

25°C

35°C

45°C

55°C

(f)

q / nm-1

ME-4 + (C12)2DMAm158NiPAm21

25°C

35°C

45°C

55°C

(k)

x = 3 (pNiPAm)

q / nm-1

ME-3 + C12(DMAm172NiPAm32)2

25°C

35°C

45°C

55°C

(l)

I(q) / cm-1

q / nm-1

ME-4 + C12DMAm168NiPAm33

25°C

35°C

45°C

55°C

(j)

I(q) / cm-1

ME-4 + C12DMAm168DEAm27

25°C

35°C

45°C

55°C

(g) ME-4 + (C12)2DMAm158DEAm22

25°C

35°C

45°C

55°C

(h)

x = 2 (pDEAm)

ME-3 + C12(DMAm172DEAm29)2

25°C

35°C

45°C

55°C

(i)

Figure S9. (a) Forward scattering intensity, (b) molecular weight, and (c) number of surfactants

molecules per droplet as a function of temperature for the used microemulsions. The values for

ME-1 and ME-3 are higher compared to the SANS data, which can be attributed to dust in the

samples. The values for ME-4 coincide with the SANS data of the similar ME-3.

Table S6. Mass averaged molecular weight Mw determined by SLS and number of surfactants per

microemulsion droplet as a function of temperature for ME-1, ME-3, and ME-4.

T /

°C

ME-1

ME-3

ME-4

Mw / kg mol-1

Nsurf

Mw / kg mol-1

Nsurf

Mw / kg mol-1

Nsurf

146(120)

93(13)

135(11)

85(7)

108(9)

68(6)

126(8)

80(5)

117(9)

74(6)

106(7)

67(5)

128(8)

81(5)

105(7)

66(4)

90(7)

57(5)

140(9)

89(6)

114(7)

72(5)

82(5)

52(4)

208(21)

132(14)

144(14)

91(9)

93(6)

59(4)

243(19)

155(12)

204(15)

128(9)

117(8)

74(5)

256(16)

163(10)

233(14)

147(9)

157(10)

99(6)

470(30)

302(19)

560(50)

350(30)

223(14)

141(9)

1660(120)

1060(80)

3100(400)

2000(240)

410(25)

259(16)

20 30 40 50 60

10−4

10−3

10−2

20 30 40 50 60

101

102

103

20 30 40 50 60

101

102

103

ISLS(0) / cm-1

temperature / °C

ME-1

ME-3

ME-4

(a)

MSLS

w / kg mol-1

temperature / °C

(b)

Nsurf

temperature / °C

(c)

Dynamic Light Scattering (DLS)

Figure S10. Autocorrelation curves of microemulsions at 90 ° for selected temperatures of 25 °C,

35 °C, 45 °C and 55 °C for microemulsions (a) ME-1, (b) ME-3, and (c) ME-4.

10-7 10-5 10-3 10-1

0.0

0.2

0.4

0.6

0.8

1.0

1.2

10-7 10-5 10-3 10-1 10-7 10-5 10-3 10-1

g(1)(

) (90°)

/ s

ME-1 25°C

35°C

45°C

55°C

(a)

/ s

ME-3 25°C

35°C

45°C

55°C

(b)

/ s

ME-4 25°C

35°C

45°C

55°C

(c)

Figure S11. Autocorrelation curves of ME-polymer complexes at 90 ° for selected temperatures

of 25 °C, 35 °C, 45 °C and 55 °C displayed for polymers (a–c) without TR block, (d–f) with

pNPAm as TR block, (g–i) with pNiPAm as TR block, and (j–l) with pDEAm as TR block.

0.0

0.2

0.4

0.6

0.8

1.0

1.2

0.0

0.2

0.4

0.6

0.8

1.0

1.2

10-7 10-5 10-3 10-1

0.0

0.2

0.4

0.6

0.8

1.0

1.2

10-7 10-5 10-3 10-1 10-7 10-5 10-3 10-1

0.0

0.2

0.4

0.6

0.8

1.0

1.2

g(1)(

) (90°)

ME-4 + C12DMAm168

35°C

45°C

55°C

(a)

B2A

ME-4 + (C12)2DMAm158

25°C

35°C

45°C

55°C

(b)

pDMAm

BA2

ME-3 + C12(DMAm172)2

25°C

35°C

45°C

55°C

(c)

BAB*-x

g(1)(

) (90°)

ME-4 + C12DMAm127NPAm27

25°C

35°C

45°C

55°C

(d)

B2AB*-x

ME-4 + (C12)2DMAm158NPAm32

25°C

35°C

45°C

55°C

(e)

x = 1 (pNPAm)

B(AB*-x)2

ME-3 + C12(DMAm172NPAm49)2

25°C

35°C

45°C

55°C

(f)

g(1)(

) (90°)

/ s

ME-4 + C12DMAm168NiPAm33

25°C

35°C

45°C

55°C

(j)

/ s

ME-4 + (C12)2DMAm158NiPAm21

25°C

35°C

45°C

55°C

(k)

x = 3 (pNiPAm)

/ s

ME-3 + C12(DMAm172NiPAm32)2

25°C

35°C

45°C

55°C

(l)

g(1)(

) (90°)

ME-4 + C12DMAm168DEAm27

25°C

35°C

45°C

55°C

(g) ME-4 + (C12)2DMAm158DEAm22

25°C

35°C

45°C

55°C

(h)

x = 2 (pDEAm)

ME-3 + C12(DMAm172DEAm29)2

25°C

35°C

45°C

55°C

(i)

Figure S12. Size distribution of microemulsions (a) ME-1, (b) ME-3, and (c) ME-4 for

temperatures between 20 °C and 60 °C. The size distribution of three angles (60°, 90°, and 120°)

are superimposed to illustrate the angle-dependency. For a diffusive angle-dependency, the

distributions must overlap.

2.2×1022.2×1002.2×10-2

100102104

0.0

0.2

0.4

0.6

0.8

1.0

2.2×1022.2×1002.2×10-2

100102104

2.2×1022.2×1002.2×10-2

100102104

D25°C / mPa µm2

Rapp

h / nm

distribution weights

(a) ME-1

60°C

55°C

50°C

45°C

40°C

35°C

30°C

25°C

20°C

D25°C / mPa µm2

Rapp

h / nm

(b) ME-3

D25°C / mPa µm2

Rapp

h / nm

Figure S13. Size distribution for temperatures between 20 °C and 60 °C of ME–polymer

complexes for polymers (a–c) without TR block, (d–f) with pNPAm as TR block, (g–i) with

pDEAm as TR block, and (j–l) with pNiPAm as TR block. The size distribution of three angles

(60°, 90°, and 120°) are superimposed to illustrate the angle-dependency. For a diffusive angle-

dependency, the distributions must overlap.

100102104

0.0

0.2

0.4

0.6

0.8

1.0

100102104100102104

0.0

0.2

0.4

0.6

0.8

1.0

0.0

0.2

0.4

0.6

0.8

1.0

2.2×1022.2×1002.2×10-2

0.0

0.2

0.4

0.6

0.8

1.0

2.2×1022.2×1002.2×10-2 2.2×1022.2×1002.2×10-2

Rapp

h / nm

distribution weights

(a)

60°C

55°C

50°C

45°C

40°C

35°C

30°C

25°C

20°C

ME-4 + C12DMAm168

Rapp

h / nm

ME-4 + (C12)2DMAm158

(b)

pDMAm

Rapp

h / nm

ME-3 + C12(DMAm172)2

(c)

BAB*-x

distribution weights

ME-4 + C12DMAm127NPAm27

(d)

60°C

55°C

50°C

45°C

40°C

35°C

30°C

25°C

20°C

B2AB*-x

ME-4 + (C12)2DMAm158NPAm32

(e)

x = 1 (pNPAm)

B(AB*-x)2

ME-3 + C12(DMAm172NPAm49)2

(f)

distribution weights

ME-4 + C12DMAm168DEAm27

(g)

60°C

55°C

50°C

45°C

40°C

35°C

30°C

25°C

20°C

ME-4 + (C12)2DMAm158DEAm22

(h)

x = 2 (pDEAm)

ME-3 + C12(DMAm172DEAm29)2

(i)

D25°C / mPa µm2

distribution weights

(j) ME-4 + C12DMAm168NiPAm33

60°C

55°C

50°C

45°C

40°C

35°C

30°C

25°C

20°C

D25°C / mPa µm2

ME-4 + (C12)2DMAm158NiPAm21

(k)

D25°C / mPa µm2

x = 3 (pNiPAm)

ME-3 + C12(DMAm172NiPAm32)2

(l)

SMALL-ANGLE NEUTRON SCATTERING (SANS)

Estimation of molecular weight of microemulsion droplets

The mass averaged molecular weight Mw given in Table 1 was determined via I(0) obtained from

the SANS data by averaging the intensity plateau values at low q. The mass averaged molecular

weight (𝑀w) was estimated via

𝑀w=𝐼(0)

𝑆(0)⋅𝐾⋅𝑐g (S3)

with 𝐾=(𝑆𝐿𝐷sol−𝑆𝐿𝐷ME)2(𝜌ME

2𝑁A)⁄ , where K is the contrast factor, 𝑆𝐿𝐷sol the scattering

length density of the solvent, 𝑆𝐿𝐷ME averaged scattering length density of the ME, 𝜌ME averaged

density of the ME, 𝑐g the mass concentration of the microemulsion, 𝑆(0) the structure factor at

𝑞=0, , and 𝑁A the Avogadro constant. The structure factor at 𝑞=0, 𝑆(0), was estimated from

the fitted structure factor at q = 0, 𝑆shs(0).

Ellipsoidal core-shell model

The SANS data were analyzed with simple ellipsoidal core-shell model with a hard-sphere

interaction potential. The scattering intensity 𝐼csh(𝑞) is defined as

𝐼csh(𝑞)=𝜙ME

𝑉dry ⋅𝑃csh(𝑞)⋅𝑆shs(𝑞)+𝐼p(𝑞)+𝐼bkg (S4)

where 𝜙ME is the volume fraction of the microemulsion components (surfactant, cosurfactant, and

oil), 𝑉dry the dry volume of the ME droplets, 𝑞 the modulus of the scattering vector, 𝑃csh(𝑞) the

ellipsoidal core-shell form factor, 𝑆shs(𝑞) the sticky hard-sphere structure factor by Baxter (1968)2

, 𝐼p(𝑞) the scattering intensity of the added polymer, and 𝐼bkg the incoherently scattered

background. The ellipsoidal core-shell form factor 𝑃csh(𝑞) is defined as the orientational average

of the squared ellipsoidal core-shell scattering amplitude 𝐴csh(𝑞,𝜑):

𝑃csh(𝑞)=∫𝐴csh(𝑞,𝜑′)2⋅sin(𝜑′)d𝜑′

𝜋

0 (S5)

The ellipsoidal core-shell scattering amplitude 𝐴csh(𝑞,𝜑) is defined as

𝐴csh(𝑞,𝜑)=(𝑆𝐿𝐷sol−𝑆𝐿𝐷c)⋅𝑉c⋅𝐴(𝑞,𝑅(𝜑,𝑅c,𝜀))+

(𝑆𝐿𝐷sol−𝑆𝐿𝐷sh)[𝑉csh⋅𝐴(𝑞,𝑅(𝜑,𝑅csh,𝜀))−𝑉c⋅𝐴(𝑞,𝑅(𝜑,𝑅c,𝜀))] (S6)

where 𝜑 is the angle of orientation, 𝑆𝐿𝐷𝑖 the scattering length densities, 𝐴(𝑞,𝑅)=

3[sin(𝑞𝑅)−𝑞𝑅⋅cos(𝑞𝑅)]

(𝑞𝑅)3 as scattering amplitude of a sphere with radius R, 𝑅(𝜑,𝑅𝑖,𝜀)=

√𝑅𝑖2⋅sin2(𝜑)+𝑅𝑖2𝜀2⋅cos2(𝜑) the radius at the angle 𝜑 with an aspect ratio 𝜀 (𝑅𝑖 and 𝑅𝑖𝜀 refer

to the equatorial and axial radius), and 𝑉𝑖 the ellipsoid volume which is converted into the

equatorial radius via 𝑅𝑖=√3𝑉𝑖

4𝜋𝜀

3. The indices ‘sol’, ‘c’, ‘sh’, and ‘csh’ refer to the solvent, core,

shell, and core-shell, respectively. The details for calculating the scattering length densities and

volumes of the core and shell are listed in Table S7. Finally, α is the swelling ratio by which the

volume of the shell is increased by swelling with water compared to that of the dry head group.

Table S7. Overview of the composition of the core and shell of the core-shell ellipsoid with

corresponding volumes (𝑉c, 𝑉sh) and scattering length densities (𝑆𝐿𝐷c, 𝑆𝐿𝐷sh). 𝑉n and 𝑆𝐿𝐷 values

of the components can be found in Table S1.

Segment

Composition

Volume

Scattering length density

core (c)

𝑁surf(tail)

+ 𝑁co

+ 𝑁oil

+ 𝑐(Polymer)

𝑐(ME) R-group

𝑉c

=𝑁surf𝑉n,tail +𝑁co𝑉n,co

+𝑁oil𝑉n,oil

+𝑐(Polymer)

𝑐(ME)𝑉n,R-group

𝑆𝐿𝐷c

=𝑆𝐿𝐷tail𝑁surf𝑉n,tail

𝑉c+𝑆𝐿𝐷co𝑁co𝑉n,co

𝑉c

+𝑆𝐿𝐷oil𝑁oil𝑉n,oil

𝑉c

+𝑆𝐿𝐷R-group𝑐(Polymer)

𝑐(ME)𝑉n,R-group

𝑉c

shell (sh)

𝑁surf(head)

+ 𝑁sol

𝑉sh =𝑁surf𝑉n,head ⋅(1+𝛼)

𝜌sh

=𝑆𝐿𝐷head𝑁surf𝑉n,head

𝑉sh

+𝑆𝐿𝐷sol𝑁surf𝑉n,head𝛼

𝑉sh

As the sticky hard-sphere structure factor the sticky hard-sphere structure factor2 was used which

can be written as

𝑆shs(𝑞)=1

𝐴(𝑞)2+𝐵(𝑞)2 (S7)

with 𝑥=2𝑞𝑅hs

𝐴(𝑞)=1+12𝜙hs(𝑎[sin(𝑥)−𝑥cos(𝑥)

𝑥3]+𝑏[1−cos(𝑥)

𝑥2]−𝑐[sin(𝑥)

𝑥]),

𝐵(𝑞)=12𝜙hs(𝑎[1

2𝑥−sin(𝑥)

𝑥2+1−cos(𝑥)

𝑥3]+𝑏[1

𝑥−sin(𝑥)

𝑥2]−𝑐[1−cos(𝑥)

𝑥]),

𝑎=1+2𝜙hs −𝜇

(1−𝜙hs)2,𝑏= −3𝜙hs+𝜇

2(1−𝜙hs)2,𝑐=𝜆shs

12 , and 𝜇=𝜆shs ⋅𝜙hs(1−𝜙hs) (S8)

where 𝜆shs is a parameter which controls the attractive interaction of the spheres, in which it is

zero for a purely repulsive system and increases with an increasing attractiveness. The hard-sphere

radius 𝑅hs was set to the volume equivalent spherical radius 𝑅v of the ellipsoid (𝑅v=√3𝑉csh

4𝜋

3). For

samples with added polymer, the hard-sphere radius was used as a variable parameter with a lower

bound of 𝑅v. The hard-sphere volume fraction 𝜙hs was calculated in terms of the number density

𝑁

1 (=𝜙ME

𝑉dry) of ellipsoids: 𝜙hs = 𝑁

1⋅4

3𝜋𝑅v

3𝜀. The aspect ratio reduces the excluded volume due

to interpenetration effects and the ellipsoidal shape.

The scattering intensity of the polymer is described by:

𝐼p(𝑞)=𝜙p⋅𝑉n,p⋅Δ𝑆𝐿𝐷2⋅𝑃p(𝑞) (S9)

where 𝑃p(𝑞) is the form factor of a polymer chain with excluded volume, Δ𝑆𝐿𝐷 the scattering

length density difference between solvent (𝑆𝐿𝐷sol) and polymer (𝑆𝐿𝐷p) (the values are listed in

Table S3), and 𝜙p and 𝑉n,p the volume fraction and molecular volume of the polymer, respectively.

The form factor 𝑃p(𝑞) 3 is defined as

𝑃p(𝑞)=( 1

𝜈p𝑈1/2𝜈p⋅𝛾(1

2𝜈p,𝑈)−1

𝜈p𝑈1/𝜈p⋅𝛾(1

𝜈p,𝑈)) (S10)

with 𝛾(𝑠,𝑥)=∫𝑡𝑠−1e−𝑡d𝑡

𝑥

0 as incomplete gamma function. The variable 𝑈 is defined as

𝑈=𝑞2𝑎2𝑛2𝜈p

6=𝑞2𝑅g

2(2𝜈p+1)(2𝜈p+2)

6 (S11)

where q is the modulus of the scattering vector, 𝑎 the statistical segment length, 𝑛 the degree of

polymerization, and 𝜈p=1/𝑓p the excluded volume parameter, where 𝑓p equals the mass fractal

dimension of the polymer coil. U can be expressed depending on 𝑞, 𝑓p and the radius of gyration

𝑅g.

Table S8. Radius of gyration Rg and the polymer mass fractal dimension fp at 25 °C and 55 °C

used for the polymer form factor 𝑃p(𝑞) (taken from Prause et al. (2022)1). The end-to-end distance

Ree was estimated based on 𝑅ee ≈𝑅𝑔√6.

Polymer

Rg / nm

Ree / nm

25 °C

55 °C

25 °C

55 °C

25 °C

55 °C

5.9

5.4

1.62

1.71

14.5

13.2

B2A

5.3

1.88

1.85

13.0

BA2

8.4

7.0

1.61

1.77

20.6 (a)

17.1 (a)

BAB*-1

3.9

6.1

2.26

1.81

9.6

14.9

B2AB*-1

4.9

5.3

2.11

2.10

12.0

13.0

B(AB*-1)2

7.6

10.4

1.92

1.73

18.6 (a)

25.5 (a)

BAB*-2

4.3

3.9

2.09

2.38

10.5

9.6

B2AB*-2

4.4

5.3

2.24

2.38

10.8

13.0

B(AB*-2)2

6.4

6.0

1.99

2.20

15.7 (a)

14.7 (a)

BAB*-3

5.1

4.7

1.88

2.04

12.5

11.5

B2AB*-3

5.4

6.6

1.98

2.25

13.2

16.2

B(AB*-3)2

8.4

9.4

1.74

1.71

20.6 (a)

23.0 (a)

(a) The end-to-end distance for the B(AB*)2 architecture corresponds to the distance between the

end of the two B* blocks.

Figure S14. SANS data of pure microemulsions normalized to the volume fraction of

microemulsion for (a) ME-1, (b) ME-2, and (c) ME-3 displayed for 25 °C and 55 °C. The solid

black lines represent the fits (q range for fits up to 1.5 nm-1) of the ellipsoidal core-shell model (fit

parameters are given in Table S9).

10-2 10-1 100

10-1

100

101

102

103

10-2 10-1 10010-2 10-1 100101

(I(q) - Ibkg)/

ME / cm-1

q / nm-1

ME-1 25°C, 55°C

(a) D11

q / nm-1

ME-2 25°C, 55°C

(b) SANS2D

q / nm-1

ME-3 25°C, 55°C

Figure S15. SANS data with fits of ME–polymer mixtures at 25 °C and 55 °C containing polymers

(a–c) without TR block and (d–f) with pNPAm, (g–i) pDEAm, and (j–l) pNiPAm as TR block.

The scattering intensity is normalized to the volume fraction of the microemulsion. The solid black

lines represent the fits (q range for fits up to 1.5 nm-1) of the ellipsoidal core-shell model.

10-1

100

101

102

103

10-1

100

101

102

103

10-1

100

101

102

103

10-2 10-1 100

10-1

100

101

102

103

10-2 10-1 10010-2 10-1 100101

(I(q) - Ibkg)/

ME / cm-1

ME-1 +

C12DMAm168 (18 g L-1)

25°C, 55°C

(a) D11 SANS2D D33

B2A

ME-2 +

(C12)2DMAm158 (22 g L-1)

25°C, 55°C

(b)

pDMAm

BA2

ME-3 +

C12(DMAm172)2 (22 g L-1)

25°C, 55°C

(c)

BAB*-x

(I(q) - Ibkg)/

ME / cm-1

ME-2 +

C12DMAm127NPAm31 (22 g L-1)

25°C, 55°C

(d) SANS2D

B2AB*-x

ME-2 +

(C12)2DMAm158NPAm32 (22 g L-1)

25°C, 55°C

(e) SANS2D

x = 1 (pNPAm)

B(AB*-x)2

ME-3 +

C12(DMAm172NPAm49)2 (22 g L-1)

25°C, 55°C

(f) D33

(I(q) - Ibkg)/

ME / cm-1

ME-1 +

C12DMAm168DEAm27 (18 g L-1)

25°C, 55°C

(g) D11

ME-2 +

(C12)2DMAm158DEAm22 (22 g L-1)

25°C, 55°C

(h) SANS2D

x = 2 (pDEAm)

ME-3 +

C12(DMAm172DEAm29)2 (22 g L-1)

25°C, 55°C

(i) D33

(I(q) - Ibkg)/

ME / cm-1

q / nm-1

ME-1 +

C12DMAm168NiPAm33 (18 g L-1)

25°C, 55°C

(j) D11

q / nm-1

ME-2 +

(C12)2DMAm158NiPAm21 (22 g L-1)

25°C, 55°C

(k) SANS2D

x = 3 (pNiPAm)

q / nm-1

ME-3 +

C12(DMAm172NiPAm32)2 (22 g L-1)

25°C, 55°C

(l) D33

Figure S16. Best-fit parameters of the ellipsoidal core-shell form factor at 25 °C and 55 °C. (a–d)

The number of surfactant molecules per ME droplet Nsurf, (e–h) swelling ratio α of the ME droplet

shell, i.e., swelling of the Tween20 head group, (i–l) equatorial core-shell radius of the ME

droplets, (m–p) aspect ratio of the ME droplets (< 1: oblate, 1: sphere, > 1: prolate) for ME-1, ME-

2, and ME-3 before and after adding the three types of copolymer architectures.

100

150

200

ME-1

ME-2

ME-3

0.0

0.2

0.4

0.6

0.8

ME-1 + BA

ME-2 + BAB*-1

ME-1 + BAB*-2

ME-1 + BAB*-3

ME-2 + B2A

ME-2 + B2AB*-1

ME-2 + B2AB*-2

ME-2 + B2AB*-3

ME-3 + BA2

ME-3 + B(AB*-1)2

ME-3 + B(AB*-2)2

ME-3 + B(AB*-3)2

25°C

55°C

25°C

55°C

25°C

55°C

Nsurf

(a)

BAB*

(b)

B2AB*

(c)

B(AB*)2

(d)

(e) (f) (g) (h)

Rcsh / nm

(i) (j) (k) (l)

(m) (n) (o) (p)

Table S9. Overview of best-fit parameters of the ellipsoidal core-shell form factor. Variable

parameters were the aggregation number of surfactant molecules 𝑁surf, the aspect ratio ε, and the

swelling ratio α of the surfactant head group. The equatorial core-shell radius of the microemulsion

droplets Rcsh is computed based on the aggregation number. The fit uncertainties are ≤ 2 % or given

in parentheses as the uncertainty on the last digit.

Sample

𝑵𝐬𝐮𝐫𝐟

swelling ratio α

Rcsh / nm

aspect ratio ε

25 °C

55 °C

25 °C

55 °C

25 °C

55 °C

25 °C

55 °C

ME-1

113

3.69

3.20

6.0(3)

7.78

0.64

0.41

ME-2

75(3)

108(3)

4.71

3.90(11)

5.7(3)

7.6(4)

0.93(4)

0.48

ME-3

82(5)

156(5)

2.34(16)

1.64(8)

5.8(7)

7.9(5)

0.59(4)

0.37

ME-1 + BA

4.14

4.05

5.61(23)

6.78

0.72(3)

0.55

ME-2 + B2A

63(6)

103(13)

4.8(3)

5.0(5)

6.0(13)

8.4(16)

0.66(11)

0.41(4)

ME-3 + BA2

74(3)

101

2.95(13)

2.65(9)

5.7(5

6.7(3)

0.67(5)

0.51

ME-2 + BAB*-1

85(9)

155(15)

4.8(4)

8.0(10)

7.0(13)

11.2(20)

0.57(8)

0.38(3)

ME-2 + B2AB*-1

65(6)

118

4.5(3)

4.43(19)

5.9(13)

8.5(5)

0.68(12)

0.41

ME-3 + B(AB*-1)2

81(4)

179

2.71(16)

1.90(11)

5.6(6)

8.7(6)

0.65(5)

0.35

ME-1 + BAB*-2

4.20

3.80

5.7(3)

7.28

0.70(4)

0.49

ME-2 + B2AB*-2

63(5)

4.6(3)

5.03(18)

5.9(11)

7.4(4)

0.70(12)

0.43

ME-3 + B(AB*-2)2

74(3)

117

2.85(13)

2.31(10)

5.6(6)

7.2(4)

0.70(6)

0.45

ME-1 + BAB*-3

4.14

3.77

5.6(3)

7.26

0.71(4)

0.49

ME-2 + B2AB*-3

65(5)

4.55(23)

4.42(11)

5.9(11)

7.4(3)

0.70(11)

0.47

ME-3 + B(AB*-3)2

74(3)

125

2.92(13)

2.32(10)

5.6(6)

7.4(4)

0.69(5)

0.43

Table S10. Overview of best-fit parameters of the sticky hard-sphere structure factor. Variable

parameters were the hard-sphere radius 𝑅hs for samples with polymer, and the parameter 𝜆 which

describes the attractiveness of the hard-spheres. The fit uncertainties are given for the last digit in

parentheses.

Sample

𝑹𝐡𝐬 / nm

𝝀𝐬𝐡𝐬

25 °C

55 °C

25 °C

55 °C

ME-1

5.13(5)

5.82(13)

0.9(3)

2.30(11)

ME-2

5.29(21)

5.8(3)

1.6(4)

1.9(3)

ME-3

5.0(3)

5.8(3)

0.0(6)

1.7(5)

ME-1 + BA

6.26(18)

8.62(5)

1.0(3)

3.33(6)

ME-2 + B2A

6.0(8)

6.3(3)

0.7(16)

0.8(14)

ME-3 + BA2

6.0(3)

8.8(3)

3.29(13)

ME-2 + BAB*-1

5.8(7)

10.2(8)

0.4(14)

6.4(6)

ME-2 + B2AB*-1

6.1(8)

9.98(20)

0.8(16)

6.54(22)

ME-3 + B(AB*-1)2

5.8(4)

12.04(17)

12.8(4)

ME-1 + BAB*-2

6.2(3)

9.21(6)

0.9(4)

4.36(6)

ME-2 + B2AB*-2

6.2(8)

8.35(23)

0.8(15)

3.05(17)

ME-3 + B(AB*-2)2

6.0(4)

10.20(21)

0.0(8)

5.63(14)

ME-1 + BAB*-3

6.30(23)

9.23(5)

1.0(4)

4.31(6)

ME-2 + B2AB*-3

6.2(7)

8.78(17)

0.8(14)

3.28(13)

ME-3 + B(AB*-3)2

6.1(4)

10.59(19)

6.37(15)

Figure S17. SANS data with fits for ME-1–BAB* mixtures containing different polymer

concentrations at a microemulsion concentration of 41 mM (given as surfactant concentration) at

25 °C and 55 °C. (a–c) ME-1 + BA, (d–f) ME-1 + BAB*-2, and (g–i) ME-1 + BAB*-3. The

scattering intensity is normalized to the volume fraction of the microemulsion. The solid black

lines represent the fits (q range for fits up to 1.5 nm-1) of the ellipsoidal core-shell model. Data

measured at D11.

10-1

100

101

102

103

10-1

100

101

102

103

10-2 10-1 100

10-1

100

101

102

103

10-2 10-1 10010-2 10-1 100101

~4 g L-1

(I(q) - Ibkg)/

ME / cm-1

ME-1 +

C12DMAm168 (4.6 g L-1)

25°C, 55°C

(a)

~9 g L-1

ME-1 +

C12DMAm168 (8.7 g L-1)

25°C, 55°C

(b)

~18 g L-1

ME-1 +

C12DMAm168 (18 g L-1)

25°C, 55°C

(c)

(I(q) - Ibkg)/

ME / cm-1

ME-1 +

C12DMAm168DEAm27 (4.3 g L-1)

25°C, 55°C

(d)

ME-1 +

C12DMAm168DEAm27 (8.7 g L-1)

25°C, 55°C

(e)

BAB*-2

ME-1 +

C12DMAm168DEAm27 (18 g L-1)

25°C, 55°C

(f)

(I(q) - Ibkg)/

ME / cm-1

q / nm-1

ME-1 +

C12DMAm168NiPAm33 (4.1 g L-1)

25°C, 55°C

(g)

q / nm-1

ME-1 +

C12DMAm168NiPAm33 (8.7 g L-1)

25°C, 55°C

(h)

BAB*-3

q / nm-1

ME-1 +

C12DMAm168NiPAm33 (18 g L-1)

25°C, 55°C

(i)

Figure S18. Best-fit parameters of the ellipsoidal core-shell form factor for ME-1–BAB* mixtures

with different polymer concentrations at a microemulsion concentration of 41 mM (given as

surfactant concentration) at 25 °C and 55 °C. (a–d) The number of surfactant molecules per ME

droplet Nsurf, (e–h) swelling ratio α of the ME droplet shell, i.e., swelling of the Tween20 head

group, (i–l) equatorial core-shell radius of the ME droplets, (m–p) aspect ratio of the ME droplets

(< 1: oblate, 1: sphere, > 1: prolate), (q–t) hard-sphere radius, and (u–x) attraction parameter 𝜆shs

(0: purely repulsive, > 0: increasing attraction) of the hard-spheres.

100

150

200

0.0

0.2

0.4

0.6

0.8

4.6 8.7 18 4.3 8.7 18 4.1 8.7 18

25°C

55°C

ME-1

Nsurf

(a)

ME-1 + BA

(b)

ME-1 + BAB*-2

(c)

ME-1 + BAB*-3

(d)

(e) (f) (g) (h)

Rcsh / nm

(i) (j) (k) (l)

(m) (n) (o) (p)

Rhs / nm

(q)

csurf / mM

shs

(u)

(r) (s) (t)

cg / g L-1

(v)

cg / g L-1

(w)

cg / g L-1

(x)

Figure S19. SANS data with fits for ME-2–B2AB* mixtures with different microemulsion

concentrations (25 mM, 50 mM, and 100 mM; given as surfactant concentration) at a polymer

concentration of 22 g L-1 at 25 °C and 55 °C. (a–c) ME-2, (d–f) ME-2 + B2A, (g–i) ME-2 +

B2AB*-1, (j–l) ME-2 + B2AB*-2, and (m–p) ME-2 + B2AB*-3. The scattering intensity is

normalized to the volume fraction of the microemulsion. The solid black lines represent the fits (q

range for fits up to 1.5 nm-1) of the ellipsoidal core-shell model. Data measured at SANS2D.

10-1

100

101

102

103

104

10-1

100

101

102

103

104

10-1

100

101

102

103

104

10-2 10-1 100

10-1

100

101

102

103

104

10-2 10-1 10010-2 10-1 100101

10-1

100

101

102

103

104

(I(q) - Ibkg)/

ME / cm-1

ME-2 (25 mM) +

(C12)2DMAm158

25°C, 55°C

(d)

ME-2 (50 mM) +

(C12)2DMAm158

25°C, 55°C

(e)

B2A

ME-2 (100 mM) +

(C12)2DMAm158

25°C, 55°C

(f)

(I(q) - Ibkg)/

ME / cm-1

ME-2 (25 mM) +

(C12)2DMAm158NPAm32

25°C, 55°C

(g)

ME-2 (50 mM) +

(C12)2DMAm158NPAm32

25°C, 55°C

(h)

B2AB*-1

ME-2 (100 mM) +

(C12)2DMAm158NPAm32

25°C, 55°C

(i)

(I(q) - Ibkg)/

ME / cm-1

ME-2 (25 mM) +

(C12)2DMAm158DEAm22

25°C, 55°C

(j)

ME-2 (50 mM) +

(C12)2DMAm158DEAm22

25°C, 55°C

(k)

B2AB*-2

ME-2 (100 mM) +

(C12)2DMAm158DEAm22

25°C, 55°C

(l)

(I(q) - Ibkg)/

ME / cm-1

q / nm-1

ME-2 (25 mM) +

(C12)2DMAm158NiPAm21

25°C, 55°C

(m)

q / nm-1

ME-2 (50 mM) +

(C12)2DMAm158NiPAm21

25°C, 55°C

(n)

B2AB*-3

q / nm-1

ME-2 (100 mM) +

(C12)2DMAm158NiPAm21

25°C, 55°C

(p)

25 mM

(I(q) - Ibkg)/

ME / cm-1

ME-2 (25 mM)

25°C, 55°C

(a)

50 mM

ME-2 (50 mM)

25°C, 55°C

(b)

ME-2

100 mM

ME-2 (100 mM)

25°C, 55°C

(c)

Figure S20. Best-fit parameters of the ellipsoidal core-shell form factor for ME-2–B2AB*

mixtures with different microemulsion concentrations (25 mM, 50 mM, and 100 mM; given as

surfactant concentration) at a polymer concentration of 22 g L-1 at 25 °C and 55 °C. (a–e) The

number of surfactant molecules per ME droplet Nsurf, (f–j) swelling ratio α of the ME droplet shell,

i.e., swelling of the Tween20 head group, (k–o) equatorial core-shell radius of the ME droplets,

(p–t) aspect ratio of the ME droplets (< 1: oblate, 1: sphere, > 1: prolate), (u–y) hard-sphere radius,

and (z–ß) attraction parameter 𝜆shs (0: purely repulsive, > 0: increasing attraction) of the hard-

spheres.

100

150

200

0.0

0.2

0.4

0.6

0.8

25 50 100

25 50 100 25 50 100 25 50 100 25 50 100

25°C

55°C

25°C

55°C

25°C

55°C

ME-2

Nsurf

(a)

ME-2 + B2A

(b)

ME-2 + B2AB*-1

(c)

ME-2 + B2AB*-2

(d)

(f) (g) (h) (i)

Rcsh / nm

(k) (l) (m) (n)

(p) (q) (r) (s)

Rhs / nm

(u)

csurf / mM

shs

(z)

(v) (w) (x)

csurf / mM

(ä)

csurf / mM

(ö)

csurf / mM

(ü)

ME-2 + B2AB*-3

(e)

(j)

(o)

(t)

(y)

csurf / mM

(ß)

REFERENCES

(1) Prause, A.; Hechenbichler, M.; Schmidt, R. F.; Simon, M.; Prévost, S.; Cavalcanti, L. P.;

Talmon, Y.; Laschewsky, A.; Gradzielski, M. Rheological Control of Aqueous Dispersions

by Thermoresponsive BAB* Copolymers of Different Architectures. Macromolecules

2023, 56, 104–121. https://doi.org/10.1021/acs.macromol.2c01965.

(2) Baxter, R. J. Percus-Yevick Equation for Hard Spheres with Surface Adhesion. J. Chem.

Phys. 1968, 49 (6), 2770–2774. https://doi.org/10.1063/1.1670482.

(3) Hammouda, B. SANS from Homogeneous Polymer Mixtures: A Unified Overview. In

Polymer Characteristics; Springer Berlin Heidelberg: Berlin, Heidelberg, 1993; pp 87–133.

https://doi.org/10.1007/BFb0025862.