Field-directed Assembly Research Articles

Theoretical Investigation on the Metamaterials Based on the Magnetic Template-Assisted Self-Assembly of Magnetic-Plasmonic Nanoparticles for Adjustable Photonic Responses.

The assembly of artificial nano- or microstructured materials with tunable functionalities and structures, mimicking nature's complexity, holds great potential for numerous novel applications. Despite remarkable progress in synthesizing colloidal molecules with diverse functionalities, most current methods, such as the capillarity-assisted particle assembly method, the ionic assembly method based on ionic interactions, or the field-directed assembly strategy based on dipole-dipole interactions, are confined to focusing on achieving symmetrical molecules. But there have been few examples of fabricating asymmetrical colloidal molecules that could exhibit unprecedented optical properties. Here, we introduce a microfluidic and magnetic template-assisted self-assembly protocol that relies mainly on the magnetic dipole-dipole interactions between magnetized magnetic-plasmonic nanoparticles and the mechanical constraints resulting from the specially designed traps. This novel strategy not only requires no specific chemistry but also enables magnetophoretic control of magnetic-plasmonic nanoparticles during the assembly process. Moreover, the assembled asymmetrical colloidal molecules also exhibit interesting hybridized plasmon modes and produce exotic optical properties due to the strong coupling of the individual nanoparticle. The ability to fabricate asymmetrical colloidal molecules based on the bottom-up method opens up a new direction for the fabrication of novel microscale structures for biosensing, patterning, and delivery applications.

Insights into Permanent Encodings of Macroscopic Spike Patterns by Magnetic-Field-Directed Evaporative Self-Assembly from Ferrofluids.

Field-directed assembly has the potential to make large hierarchically ordered structures from nanoscale objects. Shear forces and optical, electric, and magnetic fields have been used for this purpose. Ferrofluids consist of magnetic nanoparticles hosted in mobile liquids. Though they exhibit rich structures and lattice patterns in response to an applied magnetic field, the patterns collapse when the field is removed. Recently, we adapted evaporation-induced self-assembly to obtain permanent encodings of the complex field response of magnetite nanoparticles in alkane media. The encodings are characterized by order that culminates in macrostructures comprising kinetically trapped spike patterns. The present work examines a number of variables that control pattern formation associated with this encoding. Control variables include applied magnetic field strength, magnetic field gradient, nanoparticle concentration, solvent evaporation conditions, and alkane solvent chain length. The pattern formation process is captured in six stages of evolution until the solvent host has evaporated and the pattern is permanently fixed. The macropatterns consist of hexagonal arrays that coexist with different pentagonal and heptagonal defects. The Voronoi entropy is calculated for different patterns that arise due to changes in the control parameters. Insight into order in the lattice patterns is achieved by extracting measurables like peak-to-peak spike wavelength, spike population, spike height, and base diameter from the patterns. The pattern measurables depend nonlinearly on the magnetic field gradient, solvent evaporation rate, and solvent chain length. Nanoparticle concentration does not impact the measurables significantly. Nonetheless, the results agree qualitatively with a linear expression for the critical magnetization and wavelength that explicitly contains the field gradient and surface tension.

Electric, magnetic, and shear field-directed assembly of inorganic nanoparticles.

Ordered assemblies of inorganic nanoparticles (NPs) have shown tremendous potential for wide applications due to their unique collective properties, which differ from those of individual NPs. Various assembly methods, such as external field-directed assembly, interfacial assembly, template assembly, biomolecular recognition-mediated assembly, confined assembly, and others, have been employed to generate ordered inorganic NP assemblies with hierarchical structures. Among them, the external field-directed assembly method is particularly fascinating, as it can remotely assemble NPs into well-ordered superstructures. Moreover, external fields (e.g., electric, magnetic, and shear fields) can introduce a local and/or global field intensity gradient, resulting in an additional force on NPs to drive their rotation and/or translation. Therefore, the external field-directed assembly of NPs becomes a robust method to fabricate well-defined functional materials with the desired optical, electronic, and magnetic properties, which have various applications in catalysis, sensing, disease diagnosis, energy conversion/storage, photonics, nano-floating-gate memory, and others. In this review, the effects of an electric field, magnetic field, and shear field on the organization of inorganic NPs are highlighted. The methods for controlling the well-ordered organization of inorganic NPs at different scales and their advantages are reviewed. Finally, future challenges and perspectives in this field are discussed.

Directed Assembly of Nanomaterials for Making Nanoscale Devices and Structures: Mechanisms and Applications.

Nanofabrication has been utilized to manufacture one-, two-, and three-dimensional functional nanostructures for applications such as electronics, sensors, and photonic devices. Although conventional silicon-based nanofabrication (top-down approach) has developed into a technique with extremely high precision and integration density, nanofabrication based on directed assembly (bottom-up approach) is attracting more interest recently owing to its low cost and the advantages of additive manufacturing. Directed assembly is a process that utilizes external fields to directly interact with nanoelements (nanoparticles, 2D nanomaterials, nanotubes, nanowires, etc.) and drive the nanoelements to site-selectively assemble in patterned areas on substrates to form functional structures. Directed assembly processes can be divided into four different categories depending on the external fields: electric field-directed assembly, fluidic flow-directed assembly, magnetic field-directed assembly, and optical field-directed assembly. In this review, we summarize recent progress utilizing these four processes and address how these directed assembly processes harness the external fields, the underlying mechanism of how the external fields interact with the nanoelements, and the advantages and drawbacks of utilizing each method. Finally, we discuss applications made using directed assembly and provide a perspective on the future developments and challenges.

Surface Topography-Adaptive Robotic Superstructures for Biofilm Removal and Pathogen Detection on Human Teeth.

The eradication of biofilms remains an unresolved challenge across disciplines. Furthermore, in biomedicine, the sampling of spatially heterogeneous biofilms is crucial for accurate pathogen detection and precise treatment of infection. However, current approaches are incapable of removing highly adhesive biostructures from topographically complex surfaces. To meet these needs, we demonstrate magnetic field-directed assembly of nanoparticles into surface topography-adaptive robotic superstructures (STARS) for precision-guided biofilm removal and diagnostic sampling. These structures extend or retract at multilength scales (micro-to-centimeter) to operate on opposing surfaces and rapidly adjust their shape, length, and stiffness to adapt and apply high-shear stress. STARS conform to complex surface topographies by entering angled grooves or extending into narrow crevices and “scrub” adherent biofilm with multiaxis motion while producing antibacterial reagents on-site. Furthermore, as the superstructure disrupts the biofilm, it captures bacterial, fungal, viral, and matrix components, allowing sample retrieval for multiplexed diagnostic analysis. We apply STARS using automated motion patterns to target complex three-dimensional geometries of ex vivo human teeth to retrieve biofilm samples with microscale precision, while providing “toothbrushing-like” and “flossing-like” action with antibacterial activity in real-time to achieve mechanochemical removal and multikingdom pathogen detection. This approach could lead to autonomous, multifunctional antibiofilm platforms to advance current oral care modalities and other fields contending with harmful biofilms on hard-to-reach surfaces.

Shape-encoded dynamic assembly of mobile micromachines.

Field-directed and self-propelled colloidal assembly have been used to build micromachines capable of performing complex motions and functions. However, integrating heterogeneous components into micromachines with specified structure, dynamics and function is still challenging. Here, we describe the dynamic self-assembly of mobile micromachines with desired configurations through pre-programmed physical interactions between structural and motor units. The assembly is driven by dielectrophoretic interactions, encoded in the three-dimensional shape of the individual parts. Micromachines assembled from magnetic and self-propelled motor parts exhibit reconfigurable locomotion modes and additional rotational degrees of freedom that are not available to conventional monolithic microrobots. The versatility of this site-selective assembly strategy is demonstrated on different reconfigurable, hierarchical and three-dimensional micromachine assemblies. Our results demonstrate how shape-encoded assembly pathways enable programmable, reconfigurable mobile micromachines. We anticipate that the presented design principle will advance and inspire the development of more sophisticated, modular micromachines and their integration into multiscale hierarchical systems.

Tunable colloid trajectories in nematic liquid crystals near wavy walls

The ability to dictate the motion of microscopic objects is an important challenge in fields ranging from materials science to biology. Field-directed assembly drives microparticles along paths defined by energy gradients. Nematic liquid crystals, consisting of rod-like molecules, provide new opportunities in this domain. Deviations of nematic liquid crystal molecules from uniform orientation cost elastic energy, and such deviations can be molded by bounding vessel shape. Here, by placing a wavy wall in a nematic liquid crystal, we impose alternating splay and bend distortions, and define a smoothly varying elastic energy field. A microparticle in this field displays a rich set of behaviors, as this system has multiple stable states, repulsive and attractive loci, and interaction strengths that can be tuned to allow reconfigurable states. Microparticles can transition between defect configurations, move along distinct paths, and select sites for preferred docking. Such tailored landscapes have promise in reconfigurable systems and in microrobotics applications.

Direct Visualization of Planar Assembly of Plasmonic Nanoparticles Adjacent to Electrodes in Oscillatory Electric Fields.

Electric field-directed assembly of colloidal nanoparticles (NPs) has been widely adopted for fabricating functional thin films and nanostructured surfaces. While first-order electrokinetic effects on NPs are well-understood in terms of classical models, effects of second-order electrokinetics that involve induced surface charge are still poorly understood. Induced charge electroosmotic phenomena, such as electrohydrodynamic (EHD) flow, have long been implicated in electric field-directed NP assembly with little experimental basis. Here, we use in situ dark-field optical microscopy and plasmonic NPs to directly observe the dynamics of planar assembly of colloidal NPs adjacent to a planar electrode in low-frequency (<1 kHz) oscillatory electric fields. We exploit the change in plasmonic NP color resulting from interparticle plasmonic coupling to visualize the assembly dynamics and assembly structure of silver NPs. Planar assembly of NPs is unexpected because of strong electrostatic repulsion between NPs and indicates that there are strong attractive interparticle forces oriented perpendicular to the electric field direction. A parametric investigation of the voltage- and frequency-dependent phase behavior reveals that planar NP assembly occurs over a narrow frequency range below which irreversible ballistic deposition occurs. Two key experimental observations are consistent with EHD flow-induced NP assembly: (1) NPs remain mobile during assembly and (2) electron microscopy observations reveal randomly close-packed planar assemblies, consistent with strong interparticle attraction. We interpret planar assembly in terms of EHD fluid flow and develop a scaling model that qualitatively agrees with the measured phase regions. Our results are the first direct in situ observations of EHD flow-induced NP assembly and shed light on long-standing unresolved questions concerning the formation of NP superlattices during electric field-induced NP deposition.

Electric field-directed assembly of fullerene crystal rods into hierarchical films

Self-assembly of nanomaterials with desired material properties requires assembly control from nanometer to millimeter scales.

Electric-Field-Oriented Growth of Long Hair-Like Silica Microfibrils and Derived Functional Monolithic Solids.

Controlled self-assembly using molecules/nanoparticles as building block materials represents an important approach for nanofabrication. We present a "bottom-up" fabrication approach to first grow a new class of inorganic (silica) long hair-like microfibrils or microwires and then to form monolithic solid pellet that contains parallel arrays of bundled microfibrils with a controlled orientation. During the sol-gel solution processing, reactive precursor species are utilized as molecular "building blocks" for the field-directed assembly growth of microfibrils driven by an electric field of pulsed direct current (dc) with controlled frequency. We have demonstrated a novel reactive electrofibrilation process that combines an external field with a solid-phase nucleation and growth process which in principle has no limitation on the type of reactions (such as the one here that involves sol-gel reaction chemistry) and on materials compositions (such as the example silica oxide), thus will enable bulk production of long microfibrils of wide variety of inorganic materials (other oxides or metals). Furthermore, we have fabricated uniquely architectured monolithic solid materials containing aligned microfibrils by "wet press" of the in-situ grown microfibril structure in the electric field. The consolidated monolithic slabs (1 cm × 1 cm × 3 mm) have shown anisotropic properties and desirable retention of DNA molecule fragments, thus, could serve as a platform stationary-phase materials for future development of capillary electrochromatography for biomolecule separations. Electrical field-guided self-assembly is an effective approach in producing long (hair-like) ceramic microfibrils, which can be further used in consolidation fabrication of oriented structured ceramic monoliths with potential for capillary electrophoretic chromatography and other separations applications. This original work was recorded through a patent application to understand the fibril formation mechanism and its process.

Uptake of magnetic nanoparticles for adipose-derived stem cells with multiple passage numbers

With the increasingly promising role of nanomaterials in tissue engineering and regenerative medicine, the interaction between stem cells and nanoparticles has become a critical focus. The entry of nanoparticles into cells has become a primary issue for effectively regulating the subsequent safety and performance of nanomaterials in vivo . Although the influence of nanomaterials on endocytosis has been extensively studied, reports on the influence of stem cells are rare. Moreover, the effect of nanomaterials on stem cells is also dependent upon the action mode. Unfortunately, the interaction between stem cells and assembled nanoparticles is often neglected. In this paper, we explore for the first time the uptake of γ-Fe2O3 nanoparticles by adipose-derived stem cells with different passage numbers. The results demonstrate that cellular viability decreases and cell senescence level increases with the extension of the passage number. We found the surface appearance of cellular membranes to become increasingly rough and uneven with increasing passage numbers. The iron content in the dissociative nanoparticles was also significantly reduced with increases in the passage number. However, we observed multiple-passaged stem cells cultured on assembled nanoparticles to have similarly low iron content levels. The mechanism may lie in the magnetic effect of γ-Fe2O3 nanoparticles resulting from the field-directed assembly. The results of this work will facilitate the understanding and translation of nanomaterials in the clinical application of stem cells.

Formation of printable granular and colloidal chains through capillary effects and dielectrophoresis

One-dimensional conductive particle assembly holds promise for a variety of practical applications, in particular for a new generation of electronic devices. However, synthesis of such chains with programmable shapes outside a liquid environment has proven difficult. Here we report a route to simply ‘pull’ flexible granular and colloidal chains out of a dispersion by combining field-directed assembly and capillary effects. These chains are automatically stabilized by liquid bridges formed between adjacent particles, without the need for continuous energy input or special particle functionalization. They can further be deposited onto any surface and form desired conductive patterns, potentially applicable to the manufacturing of simple electronic circuits. Various aspects of our route, including the role of particle size and the voltages needed, are studied in detail. Looking towards practical applications, we also present the possibility of two-dimensional writing, rapid solidification of chains and methods to scale up chain production.

Suppressing the Rayleigh-Plateau Instability in Field-Directed Colloidal Assembly.

Suspensions of superparamagnetic colloids that equilibrate in a toggled magnetic field undergo a Rayleigh-Plateau instability with a characteristic wavelength λ = 600 μm for the toggle frequency ν = 0.66 Hz. The instability is suppressed when the chamber length L in the field direction is less than 2λ. The final size of the magnetic domains perpendicular to the field, D, follows a power law relation of D ∼ L(0.71±0.07). These results demonstrate the structural differences of field-directed suspensions when confined to lengths scale set by the phase separation process and can potentially be used to create self-assembled colloidal crystals with well-defined size and shape.

Field-directed assembly of nanowires: identifying directors, disruptors and indices to maximize the device yield.

Individually-addressable nano-electro-mechanical (NEMS) devices have been used to demonstrate sensitive mass detection to the single-proton level, as well as neutral-particle mass spectrometry. The cost of individually securing or patterning such devices is proportional to their number or the chip area covered. This limits statistical support for new research, as well as paths to the commercial availability of extraordinarily sensitive instruments. Field-directed assembly of synthesized nanowires addresses this problem and shows potential for low-cost, large-area coverage with NEMS devices. For positive dielectrophoresis (pDEP) as the main assembly director, the space of field, geometric and material parameters is large, with combinations that can serve either as directors or disruptors for directed assembly. We seek parameter values to obtain the best yield, by introducing a rational framework to reduce trial-and-error. We show that sorting the disruptors by severity and eliminating those weakly coupled to the director, allows reduction of the parameter space. The remaining disruptors are then represented compactly by dimensionless parameters. In the example protocol chosen, a single dimensionless parameter, the yield index, allows minimization of disruptors by the choice of frequency. Following this, the voltage may be selected to maximize the yield. Using this framework, we obtained 94% pre-clamped and 88% post-clamped yield over 57000 nanowire sites. Organizing the parameter space using a director-disruptor framework, with economy introduced by non-dimensional parameters, provides a path to controllably decrease the effort and cost of manufacturing nanoscale devices. This should help in the commercialization of individually addressable nanodevices.

Field-directed chaining of nanowires: towards transparent electrodes

Nanowire networks on rigid or flexible substrates can be used as low-cost transparent electrodes for displays, photovoltaics and as sensors. Generating an ordered configuration of connected nanowires from disordered suspension requires external forces. We demonstrate chaining of nanowires, using an AC electric field to generate dielectrophoretic force on nanowires adjacent to the electrodes and dipole–dipole interaction between nanowires far from the electrodes. Classifying and controlling forces and parameters that disrupt chaining, we provide guidelines to enable large-area coverage with multiple nanowire chains. Compared with other low-cost techniques such as spray or spin coating, AC electric field-directed assembly provides control over density and connectivity of nanowire chains with potential for fabricating low-cost, high-performance devices.

Remote Giant Multispectral Plasmonic Shifts of Labile Hinged Nanorod Array via Magnetic Field.

We report a remotely mediated and fast responsive plasmonic-magnetic nanorod array with extremely large variability in optical appearance (up to 100 nm shifts in scattering maxima) and concurrently for multiple wavelengths in a broad range from UV-vis to near-infrared (at 450, 550, and 670 nm) with an external magnetic field with variable direction. The observed phenomenon demonstrates a rapid, wide-range response controlled via a noninvasive remote stimulus. The remotely controlled system suggested here is a magnetic field-directed assembly of an ordered monolayer array of unipolar oriented magnetic-plasmonic nickel-gold nanorods flexibly hinged to a sticky substrate. The unique geometry of the mobile nanorod array allows for the instant alteration of the surface plasmon polariton modes in the gold segment of the controllably tilting nanorods. This design demonstrates the utility of hybrid bimetallic nanoparticles and gives a novel approach to the design of fast-acting, remotely controlled color-changing nanomaterials for sensing and interfacial transport.

A novel magnetic hydrogel with aligned magnetic colloidal assemblies showing controllable enhancement of magnetothermal effect in the presence of alternating magnetic field.

A novel magnetic hydrogel is formed via the field-directed assembly of magnetic nanomaterials during the gelation process. The novel magnetic hydrogel exhibits direction-dependent thermogenesis in an alternating magnetic field. The specific absorption rate value in the direction along the assemblies can be 2.1-fold as much as that in the direction normal to the assemblies while the heating rate is 6-8-fold. Due to the anisotropic thermogenesis, the novel magnetic hydrogel also shows a direction-dependent release of drugs that has a 3.4-fold difference between the two directions.

Symmetry considerations for the targeted assembly of entropically stabilized colloidal crystals via Voronoi particles.

The relationship between colloidal building blocks and their assemblies is an active field of research. As a strategy for targeting novel crystal structures, we examine the use of Voronoi particles, which are hard, space-filling particles in the shape of Voronoi cells of a target structure. Although Voronoi particles stabilize their target structure in the limit of high pressure by construction, the thermodynamic assembly of the same structure at moderate pressure, close to the onset of crystallization, is not guaranteed. Indeed, we find that a more symmetric crystal is often preferred due to additional entropic contributions arising from configurational or occupational degeneracy. We characterize the assembly behavior of the Voronoi particles in terms of the symmetries of the building blocks as well as the symmetries of crystal structures and demonstrate how controlling the degeneracies through a modification of particle shape and field-directed assembly can significantly improve the assembly propensity.

Assembly of Reconfigurable Colloidal Structures by Multidirectional Field-Induced Interactions.

Field-directed colloidal assembly has shown remarkable recent progress in increasing the complexity, degree of control, and multiscale organization of the structures. This has largely been achieved by using particles of complex shapes and polarizabilites (Janus, patchy, shaped, and faceted). We review the fundamentals of the interactions leading to the directed assembly of such structures, the ways to simulate the dynamics of the process, and the effect of particle size, shape, and properties on the type of structure obtained. We discuss how directional polarization interactions induced by external electric and magnetic fields can be used to assemble complex particles or particle mixtures into lattices of tailored structure. Examples of such systems include isotropic and anisotropic shaped particles with surface patches, which form networks and crystals of unusual symmetry by dipolar, quadrupolar, and multipolar interactions in external fields. The emerging trends in making reconfigurable and dynamic structures are discussed.

Magnetic assembly-mediated enhancement of differentiation of mouse bone marrow cells cultured on magnetic colloidal assemblies.

Here we reported an interesting phenomenon that the field-induced assemblies of magnetic nanoparticles can promote the differentiation of primary mouse bone marrow cells into osteoblasts. The reason was thought to lie in the remnant magnetic interaction inside the assemblies which resulted from the magnetic field-directed assembly. Influence of the assemblies on the cells was realized by means of interface effect rather than the internalization effect. We fabricated a stripe-like assemblies array on the glass plate and cultured cells on this surface. We characterized the morphology of assemblies and measured the mechanic property as well as the magnetic property. The cellular differentiation was measured by staining and quantitative PCR. Finally, Fe uptake was excluded as the reason to cause the phenomenon.