Entropically Patchy Particles: Engineering Valence through Shape Entropy

被引:173
作者
van Anders, Greg [1 ]
Ahmed, N. Khalid [1 ]
Smith, Ross [2 ]
Engel, Michael [1 ]
Glotzer, Sharon C. [1 ,2 ]
机构
[1] Univ Michigan, Dept Chem Engn, Ann Arbor, MI 48109 USA
[2] Univ Michigan, Dept Mat Sci & Engn, Ann Arbor, MI 48109 USA
关键词
shape entropy; patchy particles; superlattices; SITE-SPECIFIC FUNCTIONALIZATION; METAL NANOPARTICLES; CHEMICAL SYNTHESIS; SURFACE-ROUGHNESS; JANUS PARTICLES; NANOCRYSTALS; COLLOIDS; CRYSTALLINE; NANOCUBES; SPHERES;
D O I
10.1021/nn4057353
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Patchy particles are a popular paradigm for the design and synthesis of nanoparticles and colloids for self-assembly. In "traditional" patchy particles, anisotropic interactions arising from patterned coatings, functionalized molecules, DNA, and other enthalpic means create the possibility for directional binding of particles into higher-ordered structures. Although the anisotropic geometry of nonspherical particles contributes to the interaction patchiness through van der Waals, electrostatic, and other interactions, how particle shape contributes entropically to self-assembly is only now beginning to be understood. The directional nature of entropic forces has recently been elucidated. A recently proposed theoretical framework that defines and quantifies directional entropic forces demonstrates the anisotropic that is, patchy nature of these emergent, attractive forces. Here we introduce the notion of entropically patchy particles as the entropic counterpart to enthalpically patchy particles. Using three example "families" of shapes, we show how to modify entropic patchiness by introducing geometric features to the particles via shape operations so as to target specific crystal structures assembled here with Monte Carlo simulations. We quantify the emergent entropic valence via a potential of mean force and torque. We show that these forces are on the order of a few k(B)T at intermediate densities below the onset of crystallization. We generalize these shape operations to shape anisotropy dimensions, in analogy with the anisotropy dimensions introduced for enthalpically patchy particles. Our findings demonstrate that entropic patchiness and emergent valence provide a way of engineering directional bonding into nanoparticle systems, whether in the presence or absence of additional, non-entropic forces.
引用
收藏
页码:931 / 940
页数:10
相关论文
共 97 条
[1]   Effect of quenched size polydispersity on the ordering transitions of hard polyhedral particles [J].
Agarwal, Umang ;
Escobedo, Fernando A. .
JOURNAL OF CHEMICAL PHYSICS, 2012, 137 (02)
[2]   Mesophase behaviour of polyhedral particles [J].
Agarwal, Umang ;
Escobedo, Fernando A. .
NATURE MATERIALS, 2011, 10 (03) :230-235
[3]   Shape-controlled synthesis of colloidal platinum nanoparticles [J].
Ahmadi, TS ;
Wang, ZL ;
Green, TC ;
Henglein, A ;
ElSayed, MA .
SCIENCE, 1996, 272 (5270) :1924-1926
[4]   Experimental Investigation of Selective Colloidal Interactions Controlled by Shape, Surface Roughness, and Steric Layers [J].
Badaire, Stephane ;
Cottin-Bizonne, Cecile ;
Stroock, Abraham D. .
LANGMUIR, 2008, 24 (20) :11451-11463
[5]   Shape selectivity in the assembly of lithographically designed colloidal particles [J].
Badaire, Stephane ;
Cottin-Bizonne, Cecile ;
Woody, Joseph W. ;
Yang, Allen ;
Stroock, Abraham D. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (01) :40-41
[6]   Using shape for self-assembly [J].
Cademartiri, Ludovico ;
Bishop, Kyle J. M. ;
Snyder, Phillip W. ;
Ozin, Geoffrey A. .
PHILOSOPHICAL TRANSACTIONS OF THE ROYAL SOCIETY A-MATHEMATICAL PHYSICAL AND ENGINEERING SCIENCES, 2012, 370 (1969) :2824-2847
[7]   Fabrication of asymmetrically coated colloid particles by microcontact printing techniques [J].
Cayre, O ;
Paunov, VN ;
Velev, OD .
JOURNAL OF MATERIALS CHEMISTRY, 2003, 13 (10) :2445-2450
[8]   Making polymeric micro- and nanoparticles of complex shapes [J].
Champion, Julie A. ;
Katare, Yogesh K. ;
Mitragotri, Samir .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2007, 104 (29) :11901-11904
[9]   Directed self-assembly of a colloidal kagome lattice [J].
Chen, Qian ;
Bae, Sung Chul ;
Granick, Steve .
NATURE, 2011, 469 (7330) :381-384
[10]   Supracolloidal Reaction Kinetics of Janus Spheres [J].
Chen, Qian ;
Whitmer, Jonathan K. ;
Jiang, Shan ;
Bae, Sung Chul ;
Luijten, Erik ;
Granick, Steve .
SCIENCE, 2011, 331 (6014) :199-202