skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: Role of Entropy in Colloidal Self-Assembly
Entropy plays a key role in the self-assembly of colloidal particles. Specifically, in the case of hard particles, which do not interact or overlap with each other during the process of self-assembly, the free energy is minimized due to an increase in the entropy of the system. Understanding the contribution of entropy and engineering it is increasingly becoming central to modern colloidal self-assembly research, because the entropy serves as a guide to design a wide variety of self-assembled structures for many technological and biomedical applications. In this work, we highlight the importance of entropy in different theoretical and experimental self-assembly studies. We discuss the role of shape entropy and depletion interactions in colloidal self-assembly. We also highlight the effect of entropy in the formation of open and closed crystalline structures, as well as describe recent advances in engineering entropy to achieve targeted self-assembled structures.  more » « less
Award ID(s):
1757371
PAR ID:
10182904
Author(s) / Creator(s):
; ;
Date Published:
Journal Name:
Entropy
Volume:
22
Issue:
8
ISSN:
1099-4300
Page Range / eLocation ID:
877
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; (, Journal of Chemical Theory and Computation)
    Self-assembly of colloidal particles is emerging as a promising approach for producing novel materials. These colloidal particles can be synthesized with protrusions (lobes) on their surfaces that allow the formation of porous structures with a wide range of applications. Using Langevin dynamics simulations, we studied self-assembly in the binary mixtures of lobed colloidal particles with variations in their lobe sizes to investigate the feasibility of using dumbbell particles (with two lobes) as cross-linkers to increase the porosity in self-assembled morphologies. Each binary system was formed by mixing the dumbbell particles with one of the following types of particles: trigonal planar (three lobes), tetrahedral (four lobes), trigonal bipyramidal (five lobes), and octahedral (six lobes). We observed that the lobe size on each particle can be tuned to favor the formation of random aggregates and spherical aggregates when the lobes are larger and well-ordered crystalline structures when the lobes are smaller. We also observed that these polydisperse systems form self-assembled structures characterized by porosities higher than those of the structures formed by the monodisperse systems. These results indicate that the lobe size is an important design feature that can be optimized to achieve desired structures with distinct morphologies and porosities, and the dumbbell particles are effective cross-linking agents to enhance the porosity in self-assembled structures. 
    more » « less
  2. ; ; (, Soft Matter)
    null (Ed.)
    Entropically driven self-assembly of hard anisotropic particles, where particle shape gives rise to emergent valencies, provides a useful perspective for the design of nanoparticle and colloidal systems. Hard particles self-assemble into a rich variety of crystal structures, ranging in complexity from simple close-packed structures to structures with 432 particles in the unit cell. Entropic crystallization of open structures, however, is missing from this landscape. Here, we report the self-assembly of a two-dimensional binary mixture of hard particles into an open host–guest structure, where nonconvex, triangular host particles form a honeycomb lattice that encapsulates smaller guest particles. Notably, this open structure forms in the absence of enthalpic interactions by effectively splitting the structure into low- and high-entropy sublattices. This is the first such structure to be reported in a two-dimensional athermal system. We discuss the observed compartmentalization of entropy in this system, and show that the effect of the size of the guest particle on the stability of the structure gives rise to a reentrant phase behavior. This reentrance suggests the possibility for a reconfigurable colloidal material, and we provide a proof-of-concept by showing the assembly behavior while changing the size of the guest particles in situ . Our findings provide a strategy for designing open colloidal crystals, as well as binary systems that exhibit co-crystallization, which have been elusive thus far. 
    more » « less
  3. ; ; (, Cell reports physical science)
    Organizing the colloidal particles into 3D superstructures is a promising strategy for fabricating functional metamaterials with novel optical, electric, and catalytic properties. The rich surface properties of the colloidal particles provide many ways to manipulate their assembly behavior. Emulsion droplets are ideal microspaces for confining colloidal self-assembly, offering many advantages such as versatility, scalability, and controllability over size, shape, and composition. In this review, we first introduce recently developed strategies for the emulsion-confined assembly of colloidal particles into 3D superstructures by manipulating the interfacial properties of the emulsion droplets and colloidal particles, then demonstrate the novel collective properties of the assembled superstructures and highlight some of their unique optical and catalytic properties and applications in bioimaging, diagnosis, drug delivery, and therapy. 
    more » « less
  4. ; ; ; (, Soft Matter)
    Entropy compartmentalization provides new self-assembly routes to colloidal host–guest (HG) struc- tures. Leveraging host particle shape to drive the assembly of HG structures has only recently been proposed and demonstrated. However, the extent to which the guest particles can dictate the structure of the porous network of host particles has not been explored. In this work, by modifying only the guest shape, we show athermal, binary mixtures of star-shaped host particles and convex polygon-shaped guest particles assemble as many as five distinct crystal structures, including rotator and discrete rotator guest crystals, two homoporous host crystals, and one heteroporous host crystal. Edge-to-edge alignment of neighboring stars results in the formation of three distinct pore motifs, whose preferential formation is controlled by the size and shape of the guest particles. Finally, we confirm, via free volume calculations, that assembly is driven by entropy compartmentalization, where the hosts and guests contribute differently to the free energy of the system; free volume calculations also explain differences in assembly based on guest shape. These results provide guest design rules for assembling colloidal HG structures, especially on surfaces and interfaces. 
    more » « less
  5. (, Biomicrofluidics)
    Manipulating the transport and assembly of colloidal particles to form segregated bands or ordered supracolloidal structures plays an important role in many aspects of science and technology, from understanding the origin of life to synthesizing new materials for next-generation manufacturing, electronics, and therapeutics. One commonly used method to direct colloidal transport and assembly is the application of electric fields, either AC or DC, due to its feasibility. However, as colloidal segregation and assembly both require active redistribution of colloidal particles across multiple length scales, it is not apparent at first sight how a DC electric field, either externally applied or internally induced, can lead to colloidal structuring. In this Perspective, we briefly review and highlight recent advances and standing challenges in colloidal transport and assembly enabled by DC electrokinetics. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email