Surface roughness directed self-assembly of patchy particles into colloidal micelles

Colloidal particles with site-specific directional interactions, so called “patchy particles”, are promising candidates for bottom-up assembly routes towards complex structures with rationally designed properties. Here we present an experimental realization of patchy colloidal particles based on material independent depletion interaction and surface roughness. Curved, smooth patches on rough colloids are shown to be exclusively attractive due to their different overlap volumes. We discuss in detail the case of colloids with one patch that serves as a model for molecular surfactants both with respect to their geometry and their interactions. These one-patch particles assemble into clusters that resemble surfactant micelles with the smooth and attractive sides of the colloids located at the interior. We term these clusters “colloidal micelles”. Direct Monte Carlo simulations starting from a homogeneous state give rise to cluster size distributions that are in good agreement with those found in experiments. Important differences with surfactant micelles originate from the colloidal character of our model system and are investigated by simulations and addressed theoretically. Our new “patchy” model system opens up the possibility for self-assembly studies into finite-sized superstructures as well as crystals with as of yet inaccessible structures.

[1]  Fumio Oosawa,et al.  Interaction between particles suspended in solutions of macromolecules , 1958 .

[2]  S. Sacanna,et al.  Lock and key colloids , 2009, Nature.

[3]  S. Glotzer,et al.  Self-Assembly of Patchy Particles. , 2004, Nano letters.

[4]  Francesco Sciortino,et al.  Theoretical and numerical study of the phase diagram of patchy colloids: ordered and disordered patch arrangements. , 2008, The Journal of chemical physics.

[5]  Joseph M. Brader,et al.  Phase behaviour and structure of model colloid-polymer mixtures , 1999 .

[6]  Sharon C. Glotzer,et al.  A precise packing sequence for self-assembled convex structures , 2007, Proceedings of the National Academy of Sciences.

[7]  F. Sciortino,et al.  A numerical study of one-patch colloidal particles: from square-well to Janus. , 2010, Physical chemistry chemical physics : PCCP.

[8]  Z. Dogic,et al.  Entropy driven self-assembly of nonamphiphilic colloidal membranes , 2010, Proceedings of the National Academy of Sciences.

[9]  D. Weitz,et al.  Synthesis of nonspherical colloidal particles with anisotropic properties. , 2006, Journal of the American Chemical Society.

[10]  Jan Groenewold,et al.  Colloidal molecules with well-controlled bond angles , 2009 .

[11]  Alfons van Blaaderen,et al.  Self-assembly of colloids with liquid protrusions. , 2009, Journal of the American Chemical Society.

[12]  M. Brenner,et al.  The Free-Energy Landscape of Clusters of Attractive Hard Spheres , 2010, Science.

[13]  Abraham D Stroock,et al.  Experimental investigation of selective colloidal interactions controlled by shape, surface roughness, and steric layers. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[14]  D. Velegol,et al.  Site-specific functionalization on individual colloids: size control, stability, and multilayers. , 2007, Langmuir.

[15]  Seung‐Man Yang,et al.  Self-organization of bidisperse colloids in water droplets. , 2005, Journal of the American Chemical Society.

[16]  F. Sciortino,et al.  Phase diagram of Janus particles. , 2009, Physical review letters.

[17]  S. Glotzer,et al.  Anisotropy of building blocks and their assembly into complex structures. , 2007, Nature materials.

[18]  J. Doye,et al.  Self-assembly of monodisperse clusters: Dependence on target geometry. , 2009, The Journal of chemical physics.

[19]  Gerhard Kahl,et al.  Self-assembly scenarios of patchy colloidal particles in two dimensions , 2010, Journal of physics. Condensed matter : an Institute of Physics journal.

[20]  T. Mason,et al.  Suppressing and enhancing depletion attractions between surfaces roughened by asperities. , 2008, Physical Review Letters.

[21]  H. Kramers Brownian motion in a field of force and the diffusion model of chemical reactions , 1940 .

[22]  C. Hall,et al.  Polymer-induced phase separations in nonaqueous colloidal suspensions , 1983 .

[23]  Liang Hong,et al.  Clusters of amphiphilic colloidal spheres. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[24]  J. Israelachvili Intermolecular and surface forces , 1985 .

[25]  W. Kegel,et al.  Patchy polymer colloids with tunable anisotropy dimensions. , 2011, The journal of physical chemistry. B.

[26]  Fumio Oosawa,et al.  On Interaction between Two Bodies Immersed in a Solution of Macromolecules , 1954 .

[27]  A. Vrij,et al.  Polymers at Interfaces and the Interactions in Colloidal Dispersions , 1976 .

[28]  Qian Chen,et al.  Directed self-assembly of a colloidal kagome lattice , 2014 .

[29]  Liang Hong,et al.  Clusters of charged Janus spheres. , 2006, Nano letters.

[30]  Abraham D Stroock,et al.  Shape selectivity in the assembly of lithographically designed colloidal particles. , 2007, Journal of the American Chemical Society.

[31]  S. Granick,et al.  Supracolloidal Reaction Kinetics of Janus Spheres , 2011, Science.

[32]  P. Bolhuis,et al.  Accurate free energies of micelle formation. , 2005, The journal of physical chemistry. B.

[33]  H. Kawaguchi,et al.  Preparation of unsymmetrical microspheres at the interfaces , 1999 .

[34]  D. Velegol,et al.  In-solution assembly of colloidal water , 2009 .

[35]  Sharon C Glotzer,et al.  Simulation studies of the self-assembly of cone-shaped particles. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[36]  E. Bianchi,et al.  Patchy colloids: state of the art and perspectives. , 2011, Physical chemistry chemical physics : PCCP.

[37]  David J Pine,et al.  Formation of anisotropic polymer colloids by disparate relaxation times. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[38]  M. Konno,et al.  Synthesis of hollow asymmetrical silica dumbbells with a movable inner core. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[39]  Phase diagram of patchy colloids: towards empty liquids. , 2006, Physical review letters.

[40]  John W. Vanderhoff,et al.  Phase separation in polystyrene latex interpenetrating polymer networks , 1990 .

[41]  D. Weitz,et al.  Colloid Surfactants for Emulsion Stabilization , 2008 .

[42]  T. Mason,et al.  Directing colloidal self-assembly through roughness-controlled depletion attractions. , 2007, Physical review letters.

[43]  Dhananjay Dendukuri,et al.  Synthesis and self-assembly of amphiphilic polymeric microparticles. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[44]  P. B. Warren,et al.  Phase Behaviour of Colloid + Polymer Mixtures , 1992 .