Harnessing Dynamic Covalent Bonds in Patchy Nanoparticles: Creating Shape-Shifting Building Blocks for Rational and Responsive Self-Assembly.

Using computational modeling, we suggest and demonstrate a novel class of building blocks for nanoparticle self-assembly, that is, shape-shifting patchy nanoparticles. These nanoparticles are designed by harnessing dynamic covalent bonds between nanoparticles and patches decorated on them. The breaking and reforming of these bonds in response to their environment allow the patches to undergo a structural rearrangement that shifts the location or number of patches. Our simulations for the assembled superstructures and kinetic pathway of two types of these building blocks demonstrate that shape-shifting patchy nanoparticles delicately meet two emerging design concepts of next generation materials: rational self-assembly and responsive matter. In this context, these nanoparticles may enable new generations of materials with reconfigurable property as well as controllable topologies in a dynamical manner.

[1]  P. Damasceno,et al.  Predictive Self-Assembly of Polyhedra into Complex Structures , 2012, Science.

[2]  Samir Mitragotri,et al.  Polymer particles that switch shape in response to a stimulus , 2010, Proceedings of the National Academy of Sciences.

[3]  Dongsheng Liu,et al.  Improving the yield of mono-DNA-functionalized gold nanoparticles through dual steric hindrance. , 2011, Journal of the American Chemical Society.

[4]  J. Vermant,et al.  Directed self-assembly of nanoparticles. , 2010, ACS nano.

[5]  Z. Tang,et al.  Self-assembly of noble metal nanocrystals: Fabrication, optical property, and application , 2012 .

[6]  Yan Gao,et al.  Manipulation of collective optical activity in one-dimensional plasmonic assembly. , 2012, ACS nano.

[7]  Zhiyong Tang,et al.  Self-Assembly of CdTe Nanocrystals into Free-Floating Sheets , 2006, Science.

[8]  Joerg Lahann,et al.  Biphasic Janus particles with nanoscale anisotropy , 2005, Nature materials.

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

[10]  M. Urban,et al.  Self-Repairing Oxetane-Substituted Chitosan Polyurethane Networks , 2009, Science.

[11]  I. Szleifer,et al.  Stimuli-responsive polymers grafted to nanopores and other nano-curved surfaces: structure, chemical equilibrium and transport , 2012 .

[12]  E. W. Meijer,et al.  Self-assembly of soft nanoparticles with tunable patchiness. , 2009, Nature nanotechnology.

[13]  Lei Jiang,et al.  Bioinspired surfaces with special wettability. , 2005, Accounts of chemical research.

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

[15]  Andreas Lendlein,et al.  Shape-memory polymers. , 2002, Angewandte Chemie.

[16]  A. Balazs,et al.  Harnessing labile bonds between nanogel particles to create self-healing materials. , 2009, ACS nano.

[17]  Yugang Zhang,et al.  The fundamental question about properties of self-assembled systems composed of inherently changeable components is discussed in the molecular dynamics computational work of Nguyen , 2011 .

[18]  S. Glotzer.  Some Assembly Required , 2004, Science.

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

[20]  S. Rowan,et al.  Using the dynamic bond to access macroscopically responsive structurally dynamic polymers. , 2011, Nature materials.

[21]  Zhiping Luo,et al.  Reversible Kirkwood-Alder transition observed in Pt3Cu2 nanoctahedron assemblies under controlled solvent annealing/drying conditions. , 2012, Journal of the American Chemical Society.

[22]  S. Glotzer,et al.  Reconfigurable assemblies of shape-changing nanorods. , 2010, ACS nano.

[23]  Z. Tang,et al.  Design and application of inorganic nanoparticle superstructures: current status and future challenges. , 2011, Small.

[24]  Oleg Gang,et al.  Continuous phase transformation in nanocube assemblies. , 2011, Physical review letters.

[25]  G. I. Bell.  Models for the specific adhesion of cells to cells. , 1978, Science.

[26]  Jie Zhang,et al.  Janus and multiblock colloidal particles. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[27]  Yan Gao,et al.  Reversible plasmonic circular dichroism of Au nanorod and DNA assemblies. , 2012, Journal of the American Chemical Society.

[28]  M. Hagan,et al.  Reconfigurable self-assembly through chiral control of interfacial tension , 2012, Nature.

[29]  Mark A. Miller,et al.  Crystallization of deformable spherical colloids. , 2010, Physical review letters.

[30]  Xu-Ming Xie,et al.  Computational modeling and simulation of nanoparticle self-assembly in polymeric systems: Structures, properties and external field effects , 2013 .

[31]  Sharon C Glotzer,et al.  Self-assembly and reconfigurability of shape-shifting particles. , 2011, ACS nano.

[32]  Xi Zhang,et al.  Amphiphilic building blocks for self-assembly: from amphiphiles to supra-amphiphiles. , 2012, Accounts of chemical research.

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

[34]  M. C. Stuart,et al.  Emerging applications of stimuli-responsive polymer materials. , 2010, Nature materials.

[35]  H. Zeng,et al.  Recent Progress in Syntheses and Applications of Dumbbell‐like Nanoparticles , 2009, Advanced materials.