Machine Learning to Reveal Nanoparticle Dynamics from Liquid-Phase TEM Videos.
ABSTRACT: Liquid-phase transmission electron microscopy (TEM) has been recently applied to materials chemistry to gain fundamental understanding of various reaction and phase transition dynamics at nanometer resolution. However, quantitative extraction of physical and chemical parameters from the liquid-phase TEM videos remains bottlenecked by the lack of automated analysis methods compatible with the videos' high noisiness and spatial heterogeneity. Here, we integrate, for the first time, liquid-phase TEM imaging with our customized analysis framework based on a machine learning model called U-Net neural network. This combination is made possible by our workflow to generate simulated TEM images as the training data with well-defined ground truth. We apply this framework to three typical systems of colloidal nanoparticles, concerning their diffusion and interaction, reaction kinetics, and assembly dynamics, all resolved in real-time and real-space by liquid-phase TEM. A diversity of properties for differently shaped anisotropic nanoparticles are mapped, including the anisotropic interaction landscape of nanoprisms, curvature-dependent and staged etching profiles of nanorods, and an unexpected kinetic law of first-order chaining assembly of concave nanocubes. These systems representing properties at the nanoscale are otherwise experimentally inaccessible. Compared to the prevalent image segmentation methods, U-Net shows a superior capability to predict the position and shape boundary of nanoparticles from highly noisy and fluctuating background-a challenge common and sometimes inevitable in liquid-phase TEM videos. We expect our framework to push the potency of liquid-phase TEM to its full quantitative level and to shed insights, in high-throughput and statistically significant fashion, on the nanoscale dynamics of synthetic and biological nanomaterials.
Project description:Numerous mechanisms have been studied for chemical reactions to provide quantitative predictions on how atoms spatially arrange into molecules. In nanoscale colloidal systems, however, less is known about the physical rules governing their spatial organization, i.e., self-assembly, into functional materials. Here, we monitor real-time self-assembly dynamics at the single nanoparticle level, which reveal marked similarities to foundational principles of polymerization. Specifically, using the prototypical system of gold triangular nanoprisms, we show that colloidal self-assembly is analogous to polymerization in three aspects: ensemble growth statistics following models for step-growth polymerization, with nanoparticles as linkable "monomers"; bond angles determined by directional internanoparticle interactions; and product topology determined by the valency of monomeric units. Liquid-phase transmission electron microscopy imaging and theoretical modeling elucidate the nanometer-scale mechanisms for these polymer-like phenomena in nanoparticle systems. The results establish a quantitative conceptual framework for self-assembly dynamics that can aid in designing future nanoparticle-based materials.Few models exist that describe the spontaneous organization of colloids into materials. Here, the authors combine liquid-phase TEM and single particle tracking to observe the dynamics of gold nanoprisms, finding that nanoscale self-assembly can be understood within the framework of atomic polymerization.
Project description:We demonstrate a generalizable strategy to use the relative trajectories of pairs and groups of nanocrystals, and potentially other nanoscale objects, moving in solution which can now be obtained by in situ liquid phase transmission electron microscopy (TEM) to determine the interaction potentials between nanocrystals. Such nanoscale interactions are crucial for collective behaviors and applications of synthetic nanocrystals and natural biomolecules, but have been very challenging to measure in situ at nanometer or sub-nanometer resolution. Here we use liquid phase TEM to extract the mathematical form of interaction potential between nanocrystals from their sampled trajectories. We show the power of this approach to reveal unanticipated features of nanocrystal-nanocrystal interactions by examining the anisotropic interaction potential between charged rod-shaped Au nanocrystals (Au nanorods); these Au nanorods assemble, in a tip-to-tip fashion in the liquid phase, in contrast to the well-known side-by-side arrangements commonly observed for drying-mediated assembly. These observations can be explained by a long-range and highly anisotropic electrostatic repulsion that leads to the tip-selective attachment. As a result, Au nanorods stay unassembled at a lower ionic strength, as the electrostatic repulsion is even longer-ranged. Our study not only provides a mechanistic understanding of the process by which metallic nanocrystals assemble but also demonstrates a method that can potentially quantify and elucidate a broad range of nanoscale interactions relevant to nanotechnology and biophysics.
Project description:The dynamics and structure of the liquid and vapor interface has remained elusive for decades due to the lack of an effective tool for directly visualization beyond micrometer resolution. Here, we designed a simple liquid-cell for encapsulating the liquid state of sodium for transmission electron microscopic (TEM) observation. The real-time dynamic structure of the liquid-vapor interface was imaged and videoed by TEM on the sample of electron irradiated sodium chloride (NaCl) crystals, a well-studied sample with low melting temperature and quantum super-shells of clusters. The nanometer resolution images exhibit the fine structures of the capillary waves, composed of first-time observed three zones of structures and features, i.e. flexible nanoscale fibers, nanoparticles/clusters, and a low-pressure area that sucks the nanoparticles from the liquid to the interface. Although the phenomenons were observed based on irradiated NaCl crystals, the similarities of the phenomenons to predictions suggest our real-time ovserved dynamic structure might be useful in validating long-debated theoretical models of the liquid-vapor interface, and enhancing our knowledge in understanding the non-equilibrium thermodynamics of the liquid-vapor interface to benefit future engineering designs in microfluidics.
Project description:Nanoparticle growth has long been a significant challenge in nanotechnology and catalysis, but the lack of knowledge on the fundamental nanoscale aspects of this process has made its understanding and prediction difficult, especially in a liquid phase. In this work, we successfully used liquid-phase transmission electron microscopy (LP-TEM) to image this process in real time at the nanometer scale, using an Au/TiO2 catalyst in the presence of NaCl(aq) as a case study. In situ LP-TEM clearly showed that the growth of Au nanoparticles occurred through a form of Ostwald ripening, whereby particles grew or disappeared, probably via monomer transfer, without clear correlation to particle size in contrast to predictions of classical Ostwald ripening models. In addition, the existence of a significant fraction of inert particles that neither grew nor shrank was observed. Furthermore, in situ transmission electron microscopy (TEM) showed that particle shrinkage was sudden and seemed a stochastic process, while particle growth by monomer attachment was slow and likely the rate-determining step for sintering in this system. Identification and understanding of these individual nanoparticle events are critical for extending the accuracy and predictive power of Ostwald ripening models for nanomaterials.
Project description:Transmission electron microscopy (TEM) has long been an essential tool for understanding the structure of materials. Over the past couple of decades, this venerable technique has undergone a number of revolutions, such as the development of aberration correction for atomic level imaging, the realization of cryogenic TEM for imaging biological specimens, and new instrumentation permitting the observation of dynamic systems in situ. Research in the latter has rapidly accelerated in recent years, based on a silicon-chip architecture that permits a versatile array of experiments to be performed under the high vacuum of the TEM. Of particular interest is using these silicon chips to enclose fluids safely inside the TEM, allowing us to observe liquid dynamics at the nanoscale. In situ imaging of liquid phase reactions under TEM can greatly enhance our understanding of fundamental processes in fields from electrochemistry to cell biology. Here, we review how in situ TEM experiments of liquids can be performed, with a particular focus on microchip-encapsulated liquid cell TEM. We will cover the basics of the technique, and its strengths and weaknesses with respect to related in situ TEM methods for characterizing liquid systems. We will show how this technique has provided unique insights into nanomaterial synthesis and manipulation, battery science and biological cells. A discussion on the main challenges of the technique, and potential means to mitigate and overcome them, will also be presented.
Project description:The ability to fabricate new materials using nanomaterials as building blocks, and with meta functionalities, is one of the most intriguing possibilities in the area of materials design and synthesis. Semiconducting quantum dots (QDs) and magnetic nanoparticles (MNPs) are co-dispersed in a liquid crystalline (LC) matrix and directed to form self-similar assemblies by leveraging the host's thermotropic phase transition. These co-assemblies, comprising 6?nm CdSe/ZnS QDs and 5-20?nm Fe3O4 MNPs, bridge nano- to micron length scales, and can be modulated in situ by applied magnetic fields <250 mT, resulting in an enhancement of QD photoluminescence (PL). This effect is reversible in co-assemblies with 5 and 10?nm MNPs but demonstrates hysteresis in those with 20?nm MNPs. Transmission electron microscopy (TEM) and energy dispersive spectroscopy reveal that at the nanoscale, while the QDs are densely packed into the center of the co-assemblies, the MNPs are relatively uniformly dispersed through the cluster volume. Using Lorentz TEM, it is observed that MNPs suspended in LC rotate to align with the applied field, which is attributed to be the cause of the observed PL increase at the micro-scale. This study highlights the critical role of correlating multiscale spectroscopy and microscopy characterization in order to clarify how interactions at the nanoscale manifest in microscale functionality.
Project description:Behavior of matter at the nanoscale differs from that of the bulk due to confinement and surface effects. Here, we report a direct observation of liquid-like behavior of a single grain boundary formed by cold-welding Au nanoparticles, 40 nm in size, by mechanical manipulation in situ TEM. The grain boundary rotates almost freely due to the free surfaces and can rotate about 90 degrees. The grain boundary sustains more stress than the bulk, confirming a strong bonding between the nanoparticles. Moreover, this technique allows the measurement of the surface diffusion coefficient from experimental observations, which we compute for the Au nanoparticles. This methodology can be used for any metal, oxide, semiconductor or combination of them.
Project description:The Linear Response Theory (LRT) is a widely accepted framework to analyze the power absorption of magnetic nanoparticles for magnetic fluid hyperthermia. Its validity is restricted to low applied fields and/or to highly anisotropic magnetic nanoparticles. Here, we present a systematic experimental analysis and numerical calculations of the specific power absorption for highly anisotropic cobalt ferrite (CoFe2O4) magnetic nanoparticles with different average sizes and in different viscous media. The predominance of Brownian relaxation as the origin of the magnetic losses in these particles is established, and the changes of the Specific Power Absorption (SPA) with the viscosity of the carrier liquid are consistent with the LRT approximation. The impact of viscosity on SPA is relevant for the design of MNPs to heat the intracellular medium during in vitro and in vivo experiments. The combined numerical and experimental analyses presented here shed light on the underlying mechanisms that make highly anisotropic MNPs unsuitable for magnetic hyperthermia.
Project description:Solution-phase self-assembly of anisotropic nanoparticles into complex 2D and 3D assemblies is one of the most promising strategies toward obtaining nanoparticle-based materials and devices with unique optical properties at the macroscale. However, controlling this process with single-particle precision is highly demanding, mostly due to insufficient understanding of the self-assembly process at the nanoscale. We report the use of in situ environmental scanning transmission electron microscopy (WetSTEM), combined with UV/vis spectroscopy, small-angle X-ray diffraction (SAXRD) and multiscale modeling, to draw a detailed picture of the dynamics of vertically aligned assemblies of gold nanorods. Detailed understanding of the self-assembly/disassembly mechanisms is obtained from real-time observations, which provide direct evidence of the colloidal stability of side-to-side nanorod clusters. Structural details and the forces governing the disassembly process are revealed with single particle resolution as well as in bulk samples, by combined experimental and theoretical modeling. In particular, this study provides unique information on the evolution of the orientational order of nanorods within side-to-side 2D assemblies and shows that both electrostatic (at the nanoscale) and thermal (in bulk) stimuli can be used to drive the process. These results not only give insight into the interactions between nanorods and the stability of their assemblies, thereby assisting the design of ordered, anisotropic nanomaterials but also broaden the available toolbox for in situ tracking of nanoparticle behavior at the single-particle level.
Project description:Highly porous, strong aerogels with anisotropic structural properties are of great interest for multifunctional materials for applications including insulators in buildings, filters for oil cleanup, electrical storage devices, etc. Contemporary aerogels are mostly extracted from fossil resources and synthesized from bottom-up techniques, often requiring additional strategies to obtain high anisotropy. In this work, a universal approach to prepare porous, strong, anisotropic aerogels is presented through exploiting the natural hierarchical and anisotropic structure of wood. The preparation comprises nanoscale removal of lignin, followed by dissolution-regeneration of nanofibers, leading to enhanced cell wall porosity with nanofibrillated networks occupying the pore space in the cellular wood structure. The aerogels retain structural anisotropy of natural wood, exhibit specific surface areas up to 247 m2/g, and show high compression strength at 95% porosity. This is a record specific area value for wood aerogels/foams and even higher than most cellulose-based aerogels for its assigned strength. The aerogel can serve as a platform for multifunctional composites including scaffolds for catalysis, gas separation, or liquid purification due to its porous matrix or as binder-free electrodes in electronics. To demonstrate the multifunctionality, the aerogels are successfully decorated with metal nanoparticles (Ag) and metal oxide nanoparticles (TiO2) by in situ synthesis, coated by the conductive polymer (PEDOT:PSS), and carbonized to yield conductive aerogels. This approach is found to be a universal way to prepare highly porous anisotropic aerogels.