Directional Statistics of Preferential Orientations of Two Shapes in Their Aggregate and Its Application to Nanoparticle Aggregation

<p>Nanoscientists have long conjectured that adjacent nanoparticles aggregate with one another in certain preferential directions during a chemical synthesis of nanoparticles, which is referred to the oriented attachment. For the study of the oriented attachment, the microscopy and nanoscience communities have used dynamic electron microscopy for direct observations of nanoparticle aggregation and have been so far relying on manual and qualitative analysis of the observations. We propose a statistical approach for studying the oriented attachment quantitatively with multiple aggregation examples in imagery observations. We abstract an aggregation by an event of two primary geometric objects merging into a secondary geometric object. We use a point set representation to describe the geometric features of the primary objects and the secondary object, and formulated the alignment of two point sets to one point set to estimate the orientation angles of the primary objects in the secondary object. The estimated angles are used as data to estimate the probability distribution of the orientation angles and test important hypotheses statistically. The proposed approach was applied for our motivating example, which demonstrated that nanoparticles of certain geometries have indeed preferential orientations in their aggregates.</p

The Mechanisms for Nanoparticle Surface Diffusion and Chain Self-Assembly Determined from Real-Time Nanoscale Kinetics in Liquid

The mechanisms for nanoparticle self-assembly are often inferred from the morphology of the final nanostructures in terms of attractive and repulsive interparticle interactions. Understanding how nanoparticle building blocks are pieced together during self-assembly is a key missing component needed to unlock new strategies and mechanistic understanding of this process. Here we use real-time nanoscale kinetics derived from liquid cell transmission electron microscopy investigation of nanoparticle self-assembly to show that nanoparticle mobility dictates the pathway for self-assembly and final nanostructure morphology. We describe a new method for modulating nanoparticle diffusion in a liquid cell, which we employ to systematically investigate the effect of mobility on self-assembly of nanoparticles. We interpret the observed diffusion in terms of electrostatically induced surface diffusion resulting from nanoparticle hopping on the liquid cell window surface. Slow-moving nanoparticles self-assemble predominantly into linear 1D chains by sequential attachment of nanoparticles to existing chains, while highly mobile nanoparticles self-assemble into chains and branched structures by chain–chain attachments. Self-assembly kinetics are consistent with a diffusion-driven mechanism; we attribute the change in self-assembly pathway to the increased self-assembly rate of highly mobile nanoparticles. These results indicate that nanoparticle mobility can dictate the self-assembly mechanism and final nanostructure morphology in a manner similar to interparticle interactions

Pearl-Like Sheen in Soft Capsules: An Unusual Optical Effect that is Reversibly Induced by Temperature

A pearl-like sheen (i.e., pearlescence) is seen in many natural materials like nacre and in some commercial paints and cosmetics. This phenomenon is attributed to the interaction of light with plate-like particles in the material. Here, for the first time, pearlescence is demonstrated in soft millimeter-scale capsules that contain no plate-like particles. The capsules have a thin (~500 µm) outer shell of N-isopropylacrylamide (NIPA) hydrogel, which has a lower critical solution temperature (LCST) of 32 °C. When a transparent NIPA-shelled capsule is heated above this LCST, it turns pearlescent. The effect is reversible, with the transparent state being recovered upon cooling. This is the first example of reversible pearlescence in any solid. Specular reflectance measurements show that the pearlescence of the capsules is comparable to that of natural pearls. Pearlescence is not observed in NIPA hydrogels; it arises only in NIPA-shelled capsules, and that too only when the shell is thin. Above its LCST, the NIPA shell shrinks and gets stretched, and nanoscale NIPA-rich domains arise within this shell, which induce the pearlescence. This study sheds fresh insight into the nature of pearlescence, on how it can be tuned, and on how this property can be introduced into various soft materials.https://doi.org/10.1002/adfm.20221310

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

Effects of Protein Unfolding on Aggregation and Gelation in Lysozyme Solutions

In this work, we investigate the role of folding/unfolding equilibrium in protein aggregation and formation of a gel network. Near the neutral pH and at a low buffer ionic strength, the formation of the gel network around unfolding conditions prevents investigations of protein aggregation. In this study, by deploying the fact that in lysozyme solutions the time of folding/unfolding is much shorter than the characteristic time of gelation, we have prevented gelation by rapidly heating the solution up to the unfolding temperature (~80 °C) for a short time (~30 min.) followed by fast cooling to the room temperature. Dynamic light scattering measurements show that if the gelation is prevented, nanosized irreversible aggregates (about 10–15 nm radius) form over a time scale of 10 days. These small aggregates persist and aggregate further into larger aggregates over several weeks. If gelation is not prevented, the nanosized aggregates become the building blocks for the gel network and define its mesh length scale. These results support our previously published conclusion on the nature of mesoscopic aggregates commonly observed in solutions of lysozyme, namely that aggregates do not form from lysozyme monomers in their native folded state. Only with the emergence of a small fraction of unfolded proteins molecules will the aggregates start to appear and grow.https://doi.org/10.3390/biom1009126

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