skip to main content

Title: Selective colloidal bonds via polymer-mediated interactions
Regioselectivity in colloidal self-assembly typically requires specific chemical interactions to guide particle binding. In this paper, we describe a new method to form selective colloidal bonds that relies solely on polymer adsorption. Mixtures of polymer-coated and bare particles are initially stable due to long-ranged electrostatic repulsion. When their charge is screened, the two species can approach each other close enough for polymer bridges to form, binding the particles together. By utilizing colloidal dumbbells, where each lobe is coated with polymer brushes of differing lengths, we demonstrate that the Debye screening length serves as a selective switch for the assembly of bare tracer particles onto the two lobes. We model the interaction using numerical self-consistent field lattice computations and show how regioselectivity arises from just a few nanometers difference in polymer brush length.
Authors:
; ; ; ;
Award ID(s):
1653465
Publication Date:
NSF-PAR ID:
10222350
Journal Name:
Soft Matter
Volume:
16
Issue:
32
Page Range or eLocation-ID:
7438 to 7446
ISSN:
1744-683X
Sponsoring Org:
National Science Foundation
More Like this
  1. In this study, we investigated hierarchical microarchitecture formation of magnetic barium hexaferrite (BF) platelets inside the polydimethylsiloxane (PDMS) matrix using electric and magnetic field colloidal assembly technique. First, external fields were applied to the colloidal solution to form the microstructure before curing the composites. After microstructure formation the composites were cured to freeze the microstructure by the application of heat. We investigated two different cases in this study-(1) magnetic field processed composites and (2) multi-field processed composites which were processed under both magnetic and electric field. We observed that macro-chains formed due to the electric and magnetic field had muchmore »higher length compared to the macro-chains formed due to the just magnetic field. For both cases individuals BHF are found to be oriented in the direction of external field. The analysis of SEM microstructures using ImageJ and MATLAB showed that at least two different level of hierarchies are present in the microstructure for both cases which can be named as BHF stacks and micro-chains. From the microstructure analysis, we found that compared to just magnetic field processed composites, the orientation of individual particles, BHF stacks and micro-chains in relation to the external field were found to be higher for the multi-field processed composites. Magneto-electro-hydrodynamics modeling of the polymer-particulate mixture predicted similar behavior. Computational simulations were performed wherein particulates, subjected to both DEP forces and additional magnetic dipole interactions, were allowed to form quasi-equilibrium structures before locking in a final structure to represent curing. Results show that dielectrophoretic (DEP) force produced from the local non-uniform electric field facilitates the translation of the platelets towards formation of chain-like structure, while external magnetic field augmented the rotation of particles inside the chain-like structure. Analysis of the simulation of microstructures confirms that multiple level of hierarchies are present in the composites microstructure for both cases, while the case with both electric and magnetic fields produced longer chains. The understanding of the hierarchical microstructure formation using the multi-field processing technique will help in the future to fabricate more complex microarchitectures with resulting multi-material properties.« less
  2. 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 structuremore »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.« less
  3. Active colloidal fluids, biological and synthetic, often demonstrate complex self-organization and the emergence of collective behavior. Spontaneous formation of multiple vortices has been recently observed in a variety of active matter systems, however, the generation and tunability of the active vortices not controlled by geometrical confinement remain challenging. Here, we exploit the persistence length of individual particles in ensembles of active rollers to tune the formation of vortices and to orchestrate their characteristic sizes. We use two systems and employ two different approaches exploiting shape anisotropy or polarization memory of individual units for control of the persistence length. We characterizemore »the dynamics of emergent multi-vortex states and reveal a direct link between the behavior of the persistence length and properties of the emergent vortices. We further demonstrate common features between the two systems including anti-ferromagnetic ordering of the neighboring vortices and active turbulent behavior with a characteristic energy cascade in the particles velocity field energy spectra. Our findings provide insights into the onset of spatiotemporal coherence in active roller systems and suggest a control knob for manipulation of dynamic self-assembly in active colloidal ensembles.« less
  4. Nanocomposite tectons (NCTs) are nanocomposite building blocks consisting of nanoparticle cores functionalized with a polymer brush, where each polymer chain terminates in a supramolecular recognition group capable of driving particle assembly. Like other ligand-driven nanoparticle assembly schemes (for example those using DNA-hybridization or solvent evaporation), NCTs are able to make colloidal crystal structures with precise particle organization in three dimensions. However, despite the similarity of NCT assembly to other methods of engineering ordered particle arrays, the crystallographic symmetries of assembled NCTs are significantly different. In this study, we provide a detailed characterization of the dynamics of hybridizations through universal (independentmore »of microscopic details) parameters. We perform rigorous free energy calculations and identify the persistence length of the ligand as the critical parameter accounting for the differences in the phase diagrams of NCTs and other assembly methods driven by hydrogen bond hybridizations. We also report new experiments to provide direct verification for the predictions. We conclude by discussing the role of non-equilibrium effects and illustrating how NCTs provide a unification of the two most successful strategies for nanoparticle assembly: solvent evaporation and DNA programmable assembly.« less
  5. We report here that dissolution and regrowth of resorcinol formaldehyde (RF) colloidal particles can occur spontaneously when they are subjected to etching in solvents such as ethanol and tetrahydrofuran, resulting in the formation of hollow nanostructures with controllable shell thickness. The hollowing process of the RF particles is attributed to their structural inhomogeneity, which results from the successive deposition of oligomers with different chain lengths during their initial growth. As the near-surface layer of RF colloids mainly consists of long-chain oligomers while the inner part consists of short-chain oligomers, selective etching removes the latter and produces the hollow structures. Bymore »revealing the important effects of the condensation degree of RF, the etching time and temperature, and the composition of solvents, we demonstrate that the morphology and structure of the resulting RF nanostructures can be conveniently and precisely controlled. This study not only improves our understanding of the structural heterogeneity of colloidal polymer particles, but also provides a practical and universal self-templated approach for the synthesis of hollow nanostructures.« less