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Designed Colloidal Self-Assembly

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A special issue of Materials (ISSN 1996-1944).

Deadline for manuscript submissions: closed (30 September 2017) | Viewed by 67940

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Dr. Andrei V. Petukhov

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van ’t Hoff laboratory for physical & colloid chemistry, Debye Institute for Nanomaterials Science, Utrecht University, The Netherlands and Laboratory of Physical Chemistry, Eindhoven University of Technology, The Netherlands
Interests: colloids and nanoparticles; self-organisation; colloidal crystals; colloidal liquid crystals; chiral colloids; active matter and dissipative assembly; advanced synchrotron scattering techniques; microscopy at the nanoscale
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Dr. Gert Jan Vroege

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Van ’t Hoff Laboratory for Physical & Colloid Chemistry, Debye Institute for Nanomaterials Science, Utrecht University, Utrecht, The Netherlands
Interests: colloidal crystals; colloidal liquid crystals; shape effects; directional interactions; magnetic particles; small-angle x-ray scattering (SAXS); external fields; theory of phase transitions

Special Issue Information

Dear Colleagues,

Self-organization of colloids is strongly affected or even driven by entropic interactions. It is a spectacular phenomenon which has attracted much attention in recent decades. Studies of colloid self-organization have enabled progress regarding fundamental questions relevant for materials science, such as nucleation, crystallization and jamming. Self-organized colloids provide large-scale templates to fabricate novel materials with unique optical properties, as well as materials for application in catalysis, sensorics and biomaterials. Increasingly, the field is inspired by biology where self-organization is one of the key principles.

This Special Issue is devoted to various techniques that allow designing colloidal assemblies with desired properties. To achieve that, one can tune interparticle interactions and use, for example, the interplay between short- and long-range interactions. One can vary the shape of the particles to change the symmetry of the colloidal assemblies. One can use patchy particles with direction-dependent interactions. One can use DNA adsorbed at the particle surface to induce specific interactions between colloids. One might also apply external fields such as electric, magnetic and/or shear fields to push the system towards the desired assembly. Finally, one can use anisotropic media such as liquid crystals to induce directional interactions between the dispersed colloidal particles. In these ways one can achieve spontaneous self-assembly of colloids into self-limiting 0D assemblies, linear 1D structures, planar 2D layers, and 3D crystals and liquid crystals. We hope that this Issue will contribute to the discussion of these and other techniques to design colloidal self-assembly.

It is our pleasure to invite you to submit a manuscript to this Special Issue. Full papers, communications, and reviews discussing the fundamental principles and applications of “Designed Colloidal Self-Assembly” are welcome.

Dr. Andrei V. Petukhov
Dr. Gert Jan Vroege
Guest Editors

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Keywords

designer colloids
directed self-assembly
colloidal crystals
colloidal liquid crystals
particle shape
DNA-mediated interactions
external fields
patchy colloids
liquid crystal matrix
multi-dimensional assemblies

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Published Papers (12 papers)

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2863 KiB

Open AccessArticle

Growth of Anisotropic Gold Nanoparticle Assemblies via Liposome Fusion

by Kouta Sugikawa, Tatsuya Kadota, Kotaro Matsuo, Kazuma Yasuhara and Atsushi Ikeda

Materials 2017, 10(11), 1317; https://doi.org/10.3390/ma10111317 - 17 Nov 2017

Cited by 5 | Viewed by 5060

Abstract

Anisotropic assembly of nanoparticles (NPs) has attracted extensive attention because of the potential applications in materials science, biology, and medicine. However, assembly control (e.g., the number of assembled NPs) has not been adequately studied. Here, the growth of anisotropic gold NP assemblies on a liposome surface is reported. Citrate-coated gold NPs adsorbed on liposome surfaces were assembled in one dimension at temperatures above the phase transition temperature of the lipid bilayer. Growth of the anisotropic assemblies depended on the heating time. Absorption spectroscopy and transmission electron microscopy revealed that the gradual growth was attributed to liposome fusion, which was strongly affected by the size of the gold NPs. This method enabled us to precisely control the number of NPs in each anisotropic assembly. These results will enable the fabrication of functional materials based on NP assemblies and enable investigations of cell functions and disease causality. Full article

(This article belongs to the Special Issue Designed Colloidal Self-Assembly)

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1327 KiB

Open AccessArticle

Modifying the Morphology of Silicon Surfaces by Laser Induced Liquid Assisted Colloidal Lithography

by Magdalena Ulmeanu, Robert L. Harniman, Petko Petkov and Michael N. R. Ashfold

Materials 2017, 10(11), 1306; https://doi.org/10.3390/ma10111306 - 14 Nov 2017

Cited by 1 | Viewed by 3597

Abstract

Single, or isolated small arrays of, spherical silica colloidal particles (with refractive index n_colloid = 1.47 and radius R = 350 nm or 1.5 μm) were placed on a silicon substrate and immersed in carbon tetrachloride (n_liquid = 1.48) or toluene (n_liquid = 1.52). Areas of the sample were then exposed to a single laser pulse (8 ps duration, wavelength λ = 355 nm), and the spatial intensity modulation of the near field in the vicinity of the particles revealed via the resulting patterning of the substrate surface. In this regime, n_colloid < n_liquid and the near-field optical intensification is concentrated at and beyond the edge of the particle. Detailed experimental characterization of the irradiated Si surface using atomic force microscopy reveals contrasting topographies. The same optical behavior is observed with both liquids, i.e., the incident laser light diverges on interaction with the colloidal particle, but the resulting interaction with the substrate is liquid dependent. Topographic analysis indicates localized ablation and patterning of the Si substrate when using toluene, whereas the patterning induced under carbon tetrachloride is on a larger scale and extends well below the original substrate surface—hinting at a laser induced photochemical contribution to the surface patterning. Full article

(This article belongs to the Special Issue Designed Colloidal Self-Assembly)

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4262 KiB

Open AccessCommunication

Assembly Modulated by Particle Position and Shape: A New Concept in Self-Assembly

by Joe W. Tavacoli, Julien Heuvingh and Olivia Du Roure

Materials 2017, 10(11), 1291; https://doi.org/10.3390/ma10111291 - 10 Nov 2017

Cited by 4 | Viewed by 4694

Abstract

In this communication we outline how the bespoke arrangements and design of micron-sized superparamagnetic shapes provide levers to modulate their assembly under homogeneous magnetic fields. We label this new approach, ‘assembly modulated by particle position and shape’ (APPS). Specifically, using rectangular lattices of superparamagnetic micron-sized cuboids, we construct distinct microstructures by adjusting lattice pitch and angle of array with respect to a magnetic field. Broadly, we find two modes of assembly: (1) immediate 2D jamming of the cuboids as they rotate to align with the applied field (rotation-induced jamming) and (2) aggregation via translation after their full alignment (dipole-dipole assembly). The boundary between these two assembly pathways is independent on field strength being solely a function of the cuboid’s dimensions, lattice pitch, and array angle with respect to field—a relationship which we capture, along with other features of the assembly process, in a ‘phase diagram’. In doing so, we set out initial design rules to build custom made assemblies. Moreover, these assemblies can be made flexible thanks to the hinged contacts of their particle building blocks. This flexibility, combined with the superparamagnetic nature of the architectures, renders our assembly method particularly appropriate for the construction of complex actuators at a scale hitherto not possible. Full article

(This article belongs to the Special Issue Designed Colloidal Self-Assembly)

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5423 KiB

Open AccessFeature PaperArticle

Low-Temperature Crystal Structures of the Hard Core Square Shoulder Model

by Alexander Gabriëlse, Hartmut Löwen and Frank Smallenburg

Materials 2017, 10(11), 1280; https://doi.org/10.3390/ma10111280 - 7 Nov 2017

Cited by 10 | Viewed by 4362

Abstract

In many cases, the stability of complex structures in colloidal systems is enhanced by a competition between different length scales. Inspired by recent experiments on nanoparticles coated with polymers, we use Monte Carlo simulations to explore the types of crystal structures that can form in a simple hard-core square shoulder model that explicitly incorporates two favored distances between the particles. To this end, we combine Monte Carlo-based crystal structure finding algorithms with free energies obtained using a mean-field cell theory approach, and draw phase diagrams for two different values of the square shoulder width as a function of the density and temperature. Moreover, we map out the zero-temperature phase diagram for a broad range of shoulder widths. Our results show the stability of a rich variety of crystal phases, such as body-centered orthogonal (BCO) lattices not previously considered for the square shoulder model. Full article

(This article belongs to the Special Issue Designed Colloidal Self-Assembly)

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1922 KiB

Open AccessCommunication

Tuning Patchy Bonds Induced by Critical Casimir Forces

by Truc A. Nguyen, Arthur Newton, Daniela J. Kraft, Peter G. Bolhuis and Peter Schall

Materials 2017, 10(11), 1265; https://doi.org/10.3390/ma10111265 - 3 Nov 2017

Cited by 13 | Viewed by 4997

Abstract

Experimental control of patchy interactions promises new routes for the assembly of complex colloidal structures, but remains challenging. Here, we investigate the role of patch width in the assembly of patchy colloidal particles assembled by critical Casimir forces. The particles are composed of a hydrophobic dumbbell with an equatorial hydrophilic polymer shell, and are synthesized to have well-defined patch-to-shell area ratios. Patch-to-patch binding is achieved in near-critical binary solvents, in which the particle interaction strength and range are controlled by the temperature-dependent solvent correlation length. Upon decreasing the patch-to-shell area ratio, we observe a pronounced change of the bonding morphology towards directed single-bonded configurations, as clearly reflected in the formation of chain-like structures. Computer simulations using an effective critical Casimir pair potential for the patches show that the morphology change results from the geometric exclusion of the increasingly thick hydrophilic particle shells. These results highlight the experimental control of patchy interactions through the engineering of the building blocks on the way towards rationally designed colloidal superstructures. Full article

(This article belongs to the Special Issue Designed Colloidal Self-Assembly)

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2304 KiB

Open AccessArticle

Assembly of 1D Granular Structures from Sulfonated Polystyrene Microparticles

by Alexander Mikkelsen, Ahmet Kertmen, Khobaib Khobaib, Michal Rajňák, Juraj Kurimský and Zbigniew Rozynek

Materials 2017, 10(10), 1212; https://doi.org/10.3390/ma10101212 - 21 Oct 2017

Cited by 8 | Viewed by 5854

Abstract

Being able to systematically modify the electric properties of nano- and microparticles opens up new possibilities for the bottom-up fabrication of advanced materials such as the fabrication of one-dimensional (1D) colloidal and granular materials. Fabricating 1D structures from individual particles offers plenty of applications ranging from electronic sensors and photovoltaics to artificial flagella for hydrodynamic propulsion. In this work, we demonstrate the assembly of 1D structures composed of individual microparticles with modified electric properties, pulled out of a liquid environment into air. Polystyrene particles were modified by sulfonation for different reaction times and characterized by dielectric spectroscopy and dipolar force measurements. We found that by increasing the sulfonation time, the values of both electrical conductivity and dielectric constant of the particles increase, and that the relaxation frequency of particle electric polarization changes, causing the measured dielectric loss of the particles to shift towards higher frequencies. We attributed these results to water adsorbed at the surface of the particles. With sulfonated polystyrene particles exhibiting a range of electric properties, we showed how the electric properties of individual particles influence the formation of 1D structures. By tuning applied voltage and frequency, we were able to control the formation and dynamics of 1D structures, including chain bending and oscillation. Full article

(This article belongs to the Special Issue Designed Colloidal Self-Assembly)

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3335 KiB

Open AccessFeature PaperArticle

Dispersions of Goethite Nanorods in Aprotic Polar Solvents

by Delphine Coursault, Ivan Dozov, Christophe Blanc, Maurizio Nobili, Laurent Dupont, Corinne Chanéac and Patrick Davidson

Materials 2017, 10(10), 1191; https://doi.org/10.3390/ma10101191 - 17 Oct 2017

Cited by 7 | Viewed by 4268

Abstract

Colloidal suspensions of anisotropic nanoparticles can spontaneously self-organize in liquid-crystalline phases beyond some concentration threshold. These phases often respond to electric and magnetic fields. At lower concentrations, usual isotropic liquids are observed but they can display very strong Kerr and Cotton-Mouton effects (i.e., field-induced particle orientation). For many examples of these colloidal suspensions, the solvent is water, which hinders most electro-optic applications. Here, for goethite (α-FeOOH) nanorod dispersions, we show that water can be replaced by polar aprotic solvents, such as N-methyl-2-pyrrolidone (NMP) and dimethylsulfoxide (DMSO), without loss of colloidal stability. By polarized-light microscopy, small-angle X-ray scattering and electro-optic measurements, we found that the nematic phase, with its field-response properties, is retained. Moreover, a strong Kerr effect was also observed with isotropic goethite suspensions in these polar aprotic solvents. Furthermore, we found no significant difference in the behavior of both the nematic and isotropic phases between the aqueous and non-aqueous dispersions. Our work shows that goethite nanorod suspensions in polar aprotic solvents, suitable for electro-optic applications, can easily be produced and that they keep all their outstanding properties. It also suggests that this solvent replacement method could be extended to the aqueous colloidal suspensions of other kinds of charged anisotropic nanoparticles. Full article

(This article belongs to the Special Issue Designed Colloidal Self-Assembly)

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8228 KiB

Open AccessArticle

Mechanics of Pickering Drops Probed by Electric Field–Induced Stress

by Alexander Mikkelsen, Paul Dommersnes, Zbigniew Rozynek, Azarmidokht Gholamipour-Shirazi, Marcio da Silveira Carvalho and Jon Otto Fossum

Materials 2017, 10(4), 436; https://doi.org/10.3390/ma10040436 - 21 Apr 2017

Cited by 12 | Viewed by 5683

Abstract

Fluid drops coated with particles, so-called Pickering drops, play an important role in emulsion and capsule applications. In this context, knowledge of mechanical properties and stability of Pickering drops are essential. Here we prepare Pickering drops via electric field-driven self-assembly. We use direct current (DC) electric fields to induce mechanical stress on these drops, as a possible alternative to the use of, for example, fluid flow fields. Drop deformation is monitored as a function of the applied electric field strength. The deformation of pure silicone oil drops is enhanced when covered by insulating polyethylene (PE) particles, whereas drops covered by conductive clay particles can also change shape from oblate to prolate. We attribute these results to changes in the electric conductivity of the drop interface after adding particles, and have developed a fluid shell description to estimate the conductivity of Pickering particle layers that are assumed to be non-jammed and fluid-like. Retraction experiments in the absence of electric fields are also performed. Particle-covered drops retract slower than particle-free drops, caused by increased viscous dissipation due to the presence of the Pickering particle layer. Full article

(This article belongs to the Special Issue Designed Colloidal Self-Assembly)

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1551 KiB

Open AccessArticle

Assembly of One-Patch Colloids into Clusters via Emulsion Droplet Evaporation

by Hai Pham Van, Andrea Fortini and Matthias Schmidt

Materials 2017, 10(4), 361; https://doi.org/10.3390/ma10040361 - 29 Mar 2017

Cited by 7 | Viewed by 5199

Abstract

We study the cluster structures of one-patch colloidal particles generated by droplet evaporation using Monte Carlo simulations. The addition of anisotropic patch–patch interaction between the colloids produces different cluster configurations. We find a well-defined category of sphere packing structures that minimize the second [...] Read more.

χ

is larger than

0.3

. For

χ < 0.3

, the uniqueness of the packing structures is lost, and several different isomers are found. A further decrease of

χ

below

0.2

leads to formation of many isomeric structures with less dense packings. Our results could provide an explanation of the occurrence of uncommon cluster configurations in the literature observed experimentally through evaporation-driven assembly. Full article

(This article belongs to the Special Issue Designed Colloidal Self-Assembly)

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3885 KiB

Open AccessArticle

Electric Field-Driven Assembly of Sulfonated Polystyrene Microspheres

by Alexander Mikkelsen, Jarosław Wojciechowski, Michal Rajňák, Juraj Kurimský, Khobaib Khobaib, Ahmet Kertmen and Zbigniew Rozynek

Materials 2017, 10(4), 329; https://doi.org/10.3390/ma10040329 - 23 Mar 2017

Cited by 21 | Viewed by 6625

Abstract

A designed assembly of particles at liquid interfaces offers many advantages for development of materials, and can be performed by various means. Electric fields provide a flexible method for structuring particles on drops, utilizing electrohydrodynamic circulation flows, and dielectrophoretic and electrophoretic interactions. In addition to the properties of the applied electric field, the manipulation of particles often depends on the intrinsic properties of the particles to be assembled. Here, we present an easy approach for producing polystyrene microparticles with different electrical properties. These particles are used for investigations into electric field-guided particle assembly in the bulk and on surfaces of oil droplets. By sulfonating polystyrene particles, we produce a set of particles with a range of dielectric constants and electrical conductivities, related to the sulfonation reaction time. The paper presents diverse particle behavior driven by electric fields, including particle assembly at different droplet locations, particle chaining, and the formation of ribbon-like structures with anisotropic properties. Full article

(This article belongs to the Special Issue Designed Colloidal Self-Assembly)

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10193 KiB

Open AccessFeature PaperReview

Nematic Liquid-Crystal Colloids

by Igor Muševič

Materials 2018, 11(1), 24; https://doi.org/10.3390/ma11010024 - 25 Dec 2017

Cited by 45 | Viewed by 10860

Abstract

This article provides a concise review of a new state of colloidal matter called nematic liquid-crystal colloids. These colloids are obtained by dispersing microparticles of different shapes in a nematic liquid crystal that acts as a solvent for the dispersed particles. The microparticles induce a local deformation of the liquid crystal, which then generates topological defects and long-range forces between the neighboring particles. The colloidal forces in nematic colloids are much stronger than the forces in ordinary colloids in isotropic solvents, exceeding thousands of k_BT per micrometer-sized particle. Of special interest are the topological defects in nematic colloids, which appear in many fascinating forms, such as singular points, closed loops, multitudes of interlinked and knotted loops or soliton-like structures. The richness of the topological phenomena and the possibility to design and control topological defects with laser tweezers make colloids in nematic liquid crystals an excellent playground for testing the basic theorems of topology. Full article

(This article belongs to the Special Issue Designed Colloidal Self-Assembly)

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1912 KiB

Open AccessFeature PaperReview

Generating Bulk-Scale Ordered Optical Materials Using Shear-Assembly in Viscoelastic Media

by Chris E. Finlayson and Jeremy J. Baumberg

Materials 2017, 10(7), 688; https://doi.org/10.3390/ma10070688 - 22 Jun 2017

Cited by 35 | Viewed by 5071

Abstract

We review recent advances in the generation of photonics materials over large areas and volumes, using the paradigm of shear-induced ordering of composite polymer nanoparticles. The hard-core/soft-shell design of these particles produces quasi-solid “gum-like” media, with a viscoelastic ensemble response to applied shear, in marked contrast to the behavior seen in colloidal and granular systems. Applying an oscillatory shearing method to sub-micron spherical nanoparticles gives elastomeric photonic crystals (or “polymer opals”) with intense tunable structural color. The further engineering of this shear-ordering using a controllable “roll-to-roll” process known as Bending Induced Oscillatory Shear (BIOS), together with the interchangeable nature of the base composite particles, opens potentially transformative possibilities for mass manufacture of nano-ordered materials, including advances in optical materials, photonics, and metamaterials/plasmonics. Full article

(This article belongs to the Special Issue Designed Colloidal Self-Assembly)

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