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

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.

Complex Nanoparticle Diffusional Motion in Liquid-Cell Transmission Electron Microscopy.

Liquid-cell transmission electron microscopy (LCTEM) is a powerful in situ videography technique that has the potential to allow us to observe solution-phase dynamic processes at the nanoscale, including imaging the diffusion and interaction of nanoparticles. Artefactual effects imposed by the irradiated and confined liquid-cell vessel alter the system from normal "bulk-like" behavior in multiple ways. These artefactual LCTEM effects will leave their fingerprints in the motion behavior of the diffusing objects, which can be revealed through careful analysis of the object-motion trajectories.

Nanoscale Mapping of Nonuniform Heterogeneous Nucleation Kinetics Mediated by Surface Chemistry.

Nucleation underlies the formation of many liquid-phase synthetic and natural materials with applications in materials chemistry, geochemistry, biophysics, and structural biology. Most liquid-phase nucleation processes are heterogeneous, occurring at specific nucleation sites at a solid-liquid interface; however, the chemical and topographical identity of these nucleation sites and how nucleation kinetics vary from site-to-site remain mysterious. Here we utilize liquid cell electron microscopy to unveil counterintuitive nanoscale nonuniformities in heterogeneous nucleation kinetics on a macroscopically uniform solid-liquid interface.

Polymerization-Induced Self-Assembly of Micelles Observed by Liquid Cell Transmission Electron Microscopy.

In this paper, we describe the use of liquid cell transmission electron microscopy (LCTEM) for inducing and imaging the formation of spherical micelles from amphiphilic block copolymers. Within the irradiated region of the liquid cell, diblock copolymers were produced which self-assembled, yielding a targeted spherical micellar phase via polymerization-induced self-assembly (PISA). Critically, we demonstrate that nanoparticle formation can be visualized in situ and that in the presence of excess monomer, nanoparticle growth occurs to yield sizes and morphologies consistent with standard PISA conditions.

The role of electron irradiation history in liquid cell transmission electron microscopy.

In situ liquid cell transmission electron microscopy (LC-TEM) allows dynamic nanoscale characterization of systems in a hydrated state. Although powerful, this technique remains impaired by issues of repeatability that limit experimental fidelity and hinder the identification and control of some variables underlying observed dynamics. We detail new LC-TEM devices that improve experimental reproducibility by expanding available imaging area and providing a platform for investigating electron flux history on the sample.

Tackling the Challenges of Dynamic Experiments Using Liquid-Cell Transmission Electron Microscopy.

Revolutions in science and engineering frequently result from the development, and wide adoption, of a new, powerful characterization or imaging technique. Beginning with the first glass lenses and telescopes in astronomy, to the development of visual-light microscopy, staining techniques, confocal microscopy, and fluorescence super-resolution microscopy in biology, and most recently aberration-corrected, cryogenic, and ultrafast (4D) electron microscopy, X-ray microscopy, and scanning probe microscopy in nanoscience. Through these developments, our perception and understanding of the physical nature of matter at length-scales beyond ordinary perception have been fundamentally transformed.

Directly Observing Micelle Fusion and Growth in Solution by Liquid-Cell Transmission Electron Microscopy.

Amphiphilic small molecules and polymers form commonplace nanoscale macromolecular compartments and bilayers, and as such are truly essential components in all cells and in many cellular processes. The nature of these architectures, including their formation, phase changes, and stimuli-response behaviors, is necessary for the most basic functions of life, and over the past half-century, these natural micellar structures have inspired a vast diversity of industrial products, from biomedicines to detergents, lubricants, and coatings. The importance of these materials and their ubiquity have made them the subject of intense investigation regarding their nanoscale dynamics with increasing interest in obtaining sufficient temporal and spatial resolution to directly observe nanoscale processes.

Colloidal Covalent Organic Frameworks.

Covalent organic frameworks (COFs) are two- or three-dimensional (2D or 3D) polymer networks with designed topology and chemical functionality, permanent porosity, and high surface areas. These features are potentially useful for a broad range of applications, including catalysis, optoelectronics, and energy storage devices. But current COF syntheses offer poor control over the material's morphology and final form, generally providing insoluble and unprocessable microcrystalline powder aggregates.

The Impact of Li Grain Size on Coulombic Efficiency in Li Batteries.

One of the most promising means to increase the energy density of state-of-the-art lithium Li-ion batteries is to replace the graphite anode with a Li metal anode. While the direct use of Li metal may be highly advantageous, at present its practical application is limited by issues related to dendrite growth and low Coulombic efficiency, CE. Here operando electrochemical scanning transmission electron microscopy (STEM) is used to directly image the deposition/stripping of Li at the anode-electrolyte interface in a Li-based battery.

Gaining Control over Radiolytic Synthesis of Uniform Sub-3-nanometer Palladium Nanoparticles: Use of Aromatic Liquids in the Electron Microscope.

Synthesizing nanomaterials of uniform shape and size is of critical importance to access and manipulate the novel structure-property relationships arising at the nanoscale, such as catalytic activity. In this work, we synthesize Pd nanoparticles with well-controlled size in the sub-3 nm range using scanning transmission electron microscopy (STEM) in combination with an in situ liquid stage. We use an aromatic hydrocarbon (toluene) as a solvent that is very resistant to high-energy electron irradiation, which creates a net reducing environment without the need for additives to scavenge oxidizing radicals.

Understanding the Role of Solvation Forces on the Preferential Attachment of Nanoparticles in Liquid.

Optimization of colloidal nanoparticle synthesis techniques requires an understanding of underlying particle growth mechanisms. Nonclassical growth mechanisms are particularly important as they affect nanoparticle size and shape distributions, which in turn influence functional properties. For example, preferential attachment of nanoparticles is known to lead to the formation of mesocrystals, although the formation mechanism is currently not well-understood.

Minimum Cost Multi-Way Data Association for Optimizing Multitarget Tracking of Interacting Objects.

This paper presents a general formulation for a minimum cost data association problem which associates data features via one-to-one, m-to-one and one-to-n links with minimum total cost of the links. A motivating example is a problem of tracking multiple interacting nanoparticles imaged on video frames, where particles can aggregate into one particle or a particle can be split into multiple particles. Many existing multitarget tracking methods are capable of tracking non-interacting targets or tracking interacting targets of restricted degrees of interactions.

Observing the growth of metal-organic frameworks by in situ liquid cell transmission electron microscopy.

Liquid cell transmission electron microscopy (LCTEM) can provide direct observations of solution-phase nanoscale materials, and holds great promise as a tool for monitoring dynamic self-assembled nanomaterials. Control over particle behavior within the liquid cell, and under electron beam irradiation, is of paramount importance for this technique to contribute to our understanding of chemistry and materials science at the nanoscale. However, this type of control has not been demonstrated for complex, organic macromolecular materials, which form the basis for all biological systems and all of polymer science, and encompass important classes of advanced porous materials.

Probing the degradation mechanisms in electrolyte solutions for Li-ion batteries by in situ transmission electron microscopy.

Development of novel electrolytes with increased electrochemical stability is critical for the next generation battery technologies. In situ electrochemical fluid cells provide the ability to rapidly and directly characterize electrode/electrolyte interfacial reactions under conditions directly relevant to the operation of practical batteries. In this paper, we have studied the breakdown of a range of inorganic/salt complexes relevant to state-of-the-art Li-ion battery systems by in situ (scanning) transmission electron microscopy ((S)TEM).

Direct observation of aggregative nanoparticle growth: kinetic modeling of the size distribution and growth rate.

Direct observations of solution-phase nanoparticle growth using in situ liquid transmission electron microscopy (TEM) have demonstrated the importance of "non-classical" growth mechanisms, such as aggregation and coalescence, on the growth and final morphology of nanocrystals at the atomic and single nanoparticle scales. To date, groups have quantitatively interpreted the mean growth rate of nanoparticles in terms of the Lifshitz-Slyozov-Wagner (LSW) model for Ostwald ripening, but less attention has been paid to modeling the corresponding particle size distribution. Here we use in situ fluid stage scanning TEM to demonstrate that silver nanoparticles grow by a length-scale dependent mechanism, where individual nanoparticles grow by monomer attachment but ensemble-scale growth is dominated by aggregation.

Segmentation, Inference and Classification of Partially Overlapping Nanoparticles.

This paper presents a method that enables automated morphology analysis of partially overlapping nanoparticles in electron micrographs. In the undertaking of morphology analysis, three tasks appear necessary: separate individual particles from an agglomerate of overlapping nano-objects; infer the particle's missing contours; and ultimately, classify the particles by shape based on their complete contours. Our specific method adopts a two-stage approach: the first stage executes the task of particle separation, and the second stage conducts simultaneously the tasks of contour inference and shape classification.

Nanoparticle shape evolution identified through multivariate statistics.

Precise morphological control of nanoparticles (NPs) has been impeded by the lack of in situ techniques enabling the observation of instantaneous growth steps. Fundamentally, understanding in NP nucleation and growth kinetics has yet to achieve. In the present research, morphological characterization is demonstrated using a novel image detection statistical approach for gold NPs.

Transgastric cecectomy in canine models: natural orifice transluminal endoscopic surgery (NOTES).

Background: Natural orifice transluminal endoscopic surgery (NOTES) for bowel resection is a challenging procedure. We studied the feasibility and safety of NOTES by performing cecectomy in dogs, which is equivalent to simple bowel resection in man.

Methods: Three dogs underwent transgastric endoscopic cecectomy with laparoscopic assistance.