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1. Chirality-Dependent Magnetization of Colloidal Squares with Offset Magnetic Dipoles

   https://doi.org/10.1021/acs.jctc.4c01342  

   Dorsey, Matthew A; Velev, Orlin D; Hall, Carol K (March 2025, Journal of Chemical Theory and Computation)

   Gagliardi, Laura (Ed.)

   Colloidal particles with anisotropic geometries and interactions display rich phase behavior and hence have the potential to serve as the basis of functional materials, which can tunably and reversibly self-assemble into different configurations. External fields are one design parameter that can be used to manipulate how systems of colloidal particles assemble with one another. One challenge in designing new materials using anisotropic colloidal particles is understanding how an individual particle’s various anisotropic features, like geometry, affect their overall self-assembly. Here, we present the results of simulation studies that explore the self-assembly of 2D colloidal squares with offset magnetic dipoles in the presence of an external field. Annealing simulations are used to measure the equilibrium-phase behavior of systems of these particles in the ground state, when the magnetic interactions dominate over the thermal forces of the system. We find that the magnetic properties of these systems are strongly influenced by the relative number of squares with opposite “handedness”, or chirality, that are present within the system. Systems of squares that contain equal numbers of either chirality are extremely responsive to the external field; a relatively weak external field is required to magnetize them. In contrast, systems that contain only one chirality of squares are significantly less responsive to the external field; a significantly stronger external field is required to elicit the same magnetic response. Ultimately, the differing macroscopic magnetic properties of these systems are related to their microscopic self- assembly in an external field. Simulation snapshots and ground state phase diagrams illustrate how the absence of opposite chirality squares prevents systems of these particles from leaving an energetically favorable antiparallel configuration in the presence of an external field. When opposite chirality squares are present, these magnetic particles assemble into a head-to-tail configuration, therefore inducing a magnetic state 

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2. Directed Assembly of Magnetic Colloidal Rods in an External Field

   https://doi.org/10.1021/acs.langmuir.4c03714  

   Dorsey, Matthew A; Hall, Carol K (February 2025, Langmuir)

   Walker, Gilbert C (Ed.)

   In fabricating new colloid-based materials via bottom-up design, particle–particle interactions are engineered to encourage the formation of the desired assemblies. One way to do this is to apply an external field, which orients magnetically polarized particles in the field direction. External fields have the advantage that they can be programmed to change in time (e.g., field rotation or toggling), tunably shifting the system away from equilibrium. Here, we apply a model for ferromagnetic colloidal rods that simulates their phase behavior in the presence of an external magnetic field with constant strength and direction. An annealing process slowly reduces the temperature during molecular dynamics simulations to estimate the system’s equilibrium configuration in the ground state when the magnetic interactions between colloidal rods dominate the thermal forces. Numerous annealing simulations are performed at various particle densities and external field strengths. In the absence of an external field, the magnetic rods assemble into antiparallel configurations. When the strength of the external field is sufficiently strong, the magnetic rods are forced to orient in the direction of the field and therefore form head-to-tail structures. The formation of a head-to-tail state is associated with a net magnetic moment that results from the collective alignment of all magnetic particles in the field direction. Furthermore, when systems of magnetic rods assemble into a head-to-tail state, they occupy more space than they do in a phase in which most rods are assembled into antiparallel configurations. Phase diagrams predict that the magnetic properties of systems of rod-like magnetic particles can switch between magnetic and nonmagnetic states by tuning not only the external field strength but also the particle density. 

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3. Dual nature of magnetic nanoparticle dispersions enables control over short-range attraction and long-range repulsion interactions

   https://doi.org/10.1038/s42004-022-00687-3  

   Al Harraq, Ahmed; Hymel, Aubry A.; Lin, Emily; Truskett, Thomas M.; Bharti, Bhuvnesh (June 2022, Communications Chemistry)

   Abstract Competition between attractive and repulsive interactions drives the formation of complex phases in colloidal suspensions. A major experimental challenge lies in decoupling independent roles of attractive and repulsive forces in governing the equilibrium morphology and long-range spatial distribution of assemblies. Here, we uncover the ‘dual nature’ of magnetic nanoparticle dispersions, particulate and continuous, enabling control of the short-range attraction and long-range repulsion (SALR) between suspended microparticles. We show that non-magnetic microparticles suspended in an aqueous magnetic nanoparticle dispersion simultaneously experience a short-range depletion attraction due to the particulate nature of the fluid in competition with an in situ tunable long-range magnetic dipolar repulsion attributed to the continuous nature of the fluid. The study presents an experimental platform for achieving in situ control over SALR between colloids leading to the formation of reconfigurable structures of unusual morphologies, which are not obtained using external fields or depletion interactions alone. 

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4. Real-time imaging of metallic supraparticle assembly during nanoparticle synthesis

   https://doi.org/10.1039/D1NR05416C  

   Wang, Mei; Park, Chiwoo; Woehl, Taylor J. (January 2022, Nanoscale)

   Observations of nanoparticle superlattice formation over minutes during colloidal nanoparticle synthesis elude description by conventional understanding of self-assembly, which theorizes superlattices require extended formation times to allow for diffusively driven annealing of packing defects. It remains unclear how nanoparticle position annealing occurs on such short time scales despite the rapid superlattice growth kinetics. Here we utilize liquid phase transmission electron microscopy to directly image the self-assembly of platinum nanoparticles into close packed supraparticles over tens of seconds during nanoparticle synthesis. Electron-beam induced reduction of an aqueous platinum precursor formed monodisperse 2–3 nm platinum nanoparticles that simultaneously self-assembled over tens of seconds into 3D supraparticles, some of which showed crystalline ordered domains. Experimentally varying the interparticle interactions ( e.g. , electrostatic, steric interactions) by changing precursor chemistry revealed that supraparticle formation was driven by weak attractive van der Waals forces balanced by short ranged repulsive steric interactions. Growth kinetic measurements and an interparticle interaction model demonstrated that nanoparticle surface diffusion rates on the supraparticles were orders of magnitude faster than nanoparticle attachment, enabling nanoparticles to find high coordination binding sites unimpeded by incoming particles. These results reconcile rapid self-assembly of supraparticles with the conventional self-assembly paradigm in which nanocrystal position annealing by surface diffusion occurs on a significantly shorter time scale than nanocrystal attachment. 

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5. Characterizing the Solvent‐Induced Inversion of Colloidal Aggregation During Electrophoretic Deposition

   https://doi.org/10.1002/admi.202201779  

   DeMoulpied, Justin_R; Killenbeck, Jessica_A; Schichtl, Zebulon_G; Sharma, Babloo; Striegler, Susanne; Coridan, Robert_H (December 2022, Advanced Materials Interfaces)

   Abstract Electrophoretic deposition (EPD) of colloidal particles is a practical system for the study of crystallization and related physical phenomena. The aggregation is driven by the electroosmotic flow fields and induced dipole moments generated by the polarization of the electrode‐particle‐electrolyte interface. Here, the electrochemical control of aggregation and repulsion in the electrophoretic deposition of colloidal microspheres is reported. The nature of the observed transition depended on the composition of the solvent, switching from electrode‐driven aggregation in water to electrical field‐driven repulsion in ethanol for otherwise identical systems of colloidal microspheres. This work uses optical microscopy‐derived particles and a recently developed particle insertion method approach to extract model‐free, effective interparticle potentials to describe the ensemble behavior of the particles as a function of the solvent and electrode potential at the electrode interface. This approach can be used to understand the phase behavior of these systems based on the observable particle positions rather than a detailed understanding of the electrode‐electrolyte microphysics. This approach enables simple predictability of the static and dynamic behaviors of functional colloid‐electrode interfaces. 

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