Multi-Shell Hollow Nanogels With

Supplementary information

Multi-Shell Hollow Nanogels with

Responsive Shell Permeability

Andreas J. Schmid1, Janine Dubbert1, Andrey A. Rudov2,3,

Jan Skov Pedersen4, Peter Lindner5,

Matthias Karg6, Igor I. Potemkin2,3* and Walter Richtering1*

1 Institute of Physical Chemistry, RWTH Aachen University, Landoltweg 2, 52056

Aachen, Germany

2 Physics Department, Lomonosov Moscow State University, 119991 Moscow,

Russian Federation

3 DWI-Leibnitz Institute for Interactive Materials e.V., 52056 Aachen, Germany

4 Interdisciplinary Nanoscience Center (iNANO) and Department of Chemistry,

Aarhus University, 8000 Aarhus, Denmark

5 Institut Laue Langevin (ILL), 71 avenue des Martyrs, 38000 Grenoble, France

6 Physical Chemistry I, University of Bayreuth, 85440 Bayreuth, Germany

*email: [email protected], [email protected]

phone: (0049)-(0)241-80-94760

fax: (0049)-(0)241-80-92327

1 Table S 1 Summary of the parameters obtained by fitting the experimental scattering curves according to the model described by equation (15). The total particle radius R is calculated according to equation (18).

Silica CS @ MP HS CSS @ MP HSS 20 °C 20 °C 40 °C 20 °C 40 °C 20 °C 40 °C 52 °C 20 °C 40 °C 52 °C 2 1 Shell 3 2 63.0 24.3 63.0 32.0 17.7 75.7 68.5 Wcore [nm] 63.0 63.0 28.6Shells 60.0 63.0 63.0 Shells Shells 0.1 64.5 0.1 48.6 56.8 0.1 0.0 σ1 [nm] 0.1 0.1 63.6 1.9 0.1 0.1 0.13 0.05444 0.13 0.2746 0.1323 σpoly 0.13 0.13 0.06838 0.1474 0.13 0.13 0.2657 0.1705 1.0 0.0 1.0 0.0 0.0 ρcore 1.0 1.0 0.0 0.0 1.0 1.0 0.0 0.0 - 29.4 78.9 1.0 26.6 70.2 75.8 Wsh,1 [nm] 9.9 66.3 1.0 66.6 12.8 66.3 - 35.1 0.1 11.8 32.1 0.1 0.2 σ2 [nm] 0.1 0.1 10.7 0.1 1.7 0.1 - 0.2494 0.7641 0.2012 0.1639 0.7857 0.9325 ρsh,1 0.6383 0.8981 0.2706 1.0070 0.2859 0.8980 - 1 0.8304 0.1068 0.02549 0.8841 0.9441 scale σpoly 0.3 0.6416 1 0.6416 0.4343 0.5835 - - 16.6 13.7 12.1 11.0 13.1 Wsh,2 [nm] 66.3 - 13.2 - 53.7 30.1 - - 38.7 22.8 39.4 44.1 0.2 σ3 [nm] 65.4 - 28.4 - 50.1 0.1 - - 0.2435 0.1708 0.1232 0.1908 1.1150 ρsh,2 0.2185 - 0.2331 - 0.1958 1.0320 - - - 16.1 - - - Wsh,3 [nm] - - - - 13.6 - - - - 38.9 - - - σ4 [nm] - - - - 36.5 - - - - 0.1211 - - - ρsh,3 - - - - 0.08608 -

-1 0 9.078 36.73 14.09 13.34 47.01 0 IL(0) [cm ] 0.2514 0 9.078 0 9.327 0 0 5.9 9.8 7.5 7.8 11.2 0 ξ [nm] 0.3 0 5.9 0 9.2 0

-6 -2 6.4 6.4 3.47 6.4 6.4 6.4 6.4 ρsolvent [x 10 Å ] 3.47 3.47 6.4 6.4 3.47 3.47

-1 0.02014 0.00292 0.0039 0.00285 0.00291 0.00017 0.00227 Iback [cm ] 0.00489 0.00388 0.00292 0.00220 0.00643 0.00455 R [nm] 63.2 270.3 129.7 248.2 252.9 127.2 319.8 236.3 159.9 307.0 306.4 245.5 158.2

2 Figure S 1 Results from SANS analysis of the crude silica nanoparticle cores. a Experimental scattering curve and b the corresponding radial density profile (r) of the silica core. The solid lines in a are fits according to the model described by equation .

A slight deviation between the fit and the experimental data is observed in the low-q- range, which can be attributed to a slight aggregation of the silica particles (compare

Figure S 1a). However, the two pronounced local minima in the scattering cure indicate a rather narrow size distribution.

3 Figure S 2 Experimental scattering curves from SANS measurements at the match point (MP) of the silica core and at full scattering contrast in D2O. Left column: Core-shell (CS) and hollow nanogels

(HS). Right column: Core-shell-shell (CSS) particles and hollow shell-shell (HSS) nanogels.

Measurements were performed at 52 °C (top row), 40 °C (middle row) and at 20 °C (bottom row).

The solid lines are fits according to the model described by equation .

4 Figure S 3 Results from SANS analysis of the hollow nanogel (HS) at 20 °C. a Experimental scattering curve and b the corresponding radial density profile at full scattering contrast in D 2O. The solid line in a is a fit according to the model described by equation with only one polymer shell.

Figure S 4 Results from SANS analysis of the hollow shell-shell nanogel (HSS) at 20 °C. a Experimental scattering curve and b the corresponding radial density profile at full scattering contrast in D2O. The solid line in a is a fit according to the model described by equation with only two polymer shells.

5 Figure S 5 Results from SANS analysis of the core-shell particle at 40 °C. a Experimental scattering curve and b the corresponding radial density profile at full scattering contrast in D2O. The solid line in a is a fit according to the model described by equation .