The Development and Atomic Structure of Zinc Oxide Crystals Grown within Polymers from Vapor Phase Precursors.

Sequential infiltration synthesis (SIS), also known as vapor phase infiltration (VPI), is a quickly expanding technique that allows growth of inorganic materials within polymers from vapor phase precursors. With an increasing materials library, which encompasses numerous organometallic precursors and polymer chemistries, and an expanding application space, the importance of understanding the mechanisms that govern SIS growth is ever increasing. In this work, we studied the growth of polycrystalline ZnO clusters and particles in three representative polymers: poly(methyl methacrylate), SU-8, and polymethacrolein using vapor phase diethyl zinc and water. Utilizing two atomic resolution methods, high-resolution scanning transmission electron microscopy and synchrotron X-ray absorption spectroscopy, we probed the evolution of ZnO nanocrystals size and crystallinity level inside the polymers with advancing cycles─from early nucleation and growth after a single cycle, through the formation of nanometric particles within the films, and to the coalescence of the particles upon polymer removal and thermal treatment. Through in situ Fourier transform infrared spectroscopy and microgravimetry, we highlight the important role of water molecules throughout the process and the polymers' hygroscopic level that leads to the observed differences in growth patterns between the polymers, in terms of particle size, dispersity, and the evolution of crystalline order. These insights expand our understanding of crystalline materials growth within polymers and enable rational design of hybrid materials and polymer-templated inorganic nanostructures.

Mechanical property estimation of sarcoma-relevant extracellular vesicles using transmission electron microscopy.

Analysis of single extracellular vesicles (EVs) has the potential to yield valuable label-free information on their morphological structure, biomarkers and therapeutic targets, though such analysis is hindered by the lack of reliable and quantitative measurements of the mechanical properties of these compliant nanoscale particles. The technical challenge in mechanical property measurements arises from the existing tools and methods that offer limited throughput, and the reported elastic moduli range over several orders of magnitude. Here, we report on a flow-based method complemented by transmission electron microscopy (TEM) imaging to provide a high throughput, whole EV deformation analysis for estimating the mechanical properties of liposarcoma-derived EVs as a function of their size. Our study includes extracting morphological data of EVs from a large dataset of 432 TEM images, with images containing single to multiple EVs, and implementing the thin-shell deformation theory. We estimated the elastic modulus, E = 0.16 ± 0.02 MPa (mean±SE) for small EVs (sEVs; 30-150 nm) and E = 0.17 ± 0.03 MPa (mean±SE) for large EVs (lEVs; >150 nm). To our knowledge, this is the first report on the mechanical property estimation of LPS-derived EVs and has the potential to establish a relationship between EV size and EV mechanical properties.

Interactive effects of ammonium sulfate and lead on alfalfa in rare earth tailings: Physiological responses and toxicity thresholds.

Ion-adsorption rare earth ore contains significant levels of leaching agents and heavy metals, leading to substantial co-contamination. This presents significant challenges for ecological rehabilitation, yet there is limited understanding of the toxicity thresholds associated with the co-contamination of ammonium sulfate (AS) and lead (Pb) on pioneer plants. Here, we investigated the toxicity thresholds of various aspects of alfalfa, including growth, ultrastructural changes, metabolism, antioxidant system response, and Pb accumulation. The results indicated that the co-contamination of AS-Pb decreased the dry weight of shoot and root by 26 %-77 % and 18 %-92 %, respectively, leading to irregular root cell morphology and nucleus disintegration. The high concentration and combined exposures to AS and Pb induced oxidative stress on alfalfa, which stimulated the defense of the antioxidative system and resulted in an increase in proline levels and a decrease in soluble sugars. Structural equation modeling analysis and integrated biomarker response elucidated that the soluble sugars, proline, and POD were the key physiological indicators of alfalfa under stresses and indicated that co-exposure induced more severe oxidative stress in alfalfa. The toxicity thresholds under single exposure were 496 (EC5), 566 (EC10), 719 (EC25), 940 (EC50) mg kg-1 for AS and 505 (EC5), 539 (EC10), 605 (EC25), 678 (EC50) mg kg-1 for Pb. This study showed that AS-Pb pollution notably influenced plant growth performance and had negative impacts on the growth processes, metabolite levels, and the antioxidant system in plants. Our findings contribute to a theoretical foundation and research necessity for evaluating ecological risks in mining areas and assessing the suitability of ecological restoration strategies.

Nanoparticle-Plant Interactions: Physico-chemical characteristics, Application Strategies, and Transmission Electron Microscopy-Based Ultrastructural Insights, with a focus on Stereological Research.

Ensuring global food security is pressing among challenges like population growth, climate change, soil degradation, and diminishing resources. Meeting the rising food demand while reducing agriculture's environmental impact requires innovative solutions. Nanotechnology, with its potential to revolutionize agriculture, offers novel approaches to these challenges. However, potential risks and regulatory aspects of nanoparticle (NP) utilization in agriculture must be considered to maximize their benefits for human health and the environment. Understanding NP-plant cell interactions is crucial for assessing risks of NP exposure and developing strategies to control NP uptake by treated plants. Insights into NP uptake mechanisms, distribution patterns, subcellular accumulation, and induced alterations in cellular architecture can be effectively drawn using transmission electron microscopy (TEM). TEM allows direct visualization of NPs within plant tissues/cells and their influence on organelles and subcellular structures at high resolution. Moreover, integrating TEM with stereological principles, which has not been previously utilized in NP-plant cell interaction assessments, provides a novel and quantitative framework to assess these interactions. Design-based stereology enhances TEM capability by enabling precise and unbiased quantification of three-dimensional structures from two-dimensional images. This combined approach offers comprehensive data on NP distribution, accumulation, and effects on cellular morphology, providing deeper insights into NP impact on plant physiology and health. This report highlights the efficient use of TEM, enhanced by stereology, in investigating diverse NP-plant tissue/cell interactions. This methodology facilitates detailed visualization of NPs and offers robust quantitative analysis, advancing our understanding of NP behavior in plant systems and their potential implications for agricultural sustainability.

Mesoscale characterization of osseointegration around an additively manufactured genistein-coated implant.

Given the hierarchical nature of bone and bone interfaces, osseointegration, namely the formation of a direct bone-implant contact, is best evaluated using a multiscale approach. However, a trade-off exists between field of view and spatial resolution, making it challenging to image large volumes with high resolution. In this study, we combine established electron microscopy techniques to probe bone-implant interfaces at the microscale and nanoscale with plasma focused ion beam-scanning electron microscopy (PFIB-SEM) tomography to evaluate osseointegration at the mesoscale. This characterization workflow is demonstrated for bone response to an additively manufactured Ti-6Al-4V implant which combines engineered porosity to facilitate bone ingrowth and surface functionalization via genistein, a phytoestrogen, to counteract bone loss in osteoporosis. SEM demonstrated new bone formation at the implant site, including in the internal implant pores. At the nanoscale, scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy confirmed the gradual nature of the bone-implant interface. By leveraging mesoscale analysis with PFIB-SEM tomography that captures large volumes of bone-implant interface with nearly nanoscale resolution, the presence of mineral ellipsoids varying in size and orientation was revealed. In addition, a well-developed lacuno-canalicular network and mineralization fronts directed both towards the implant and away from it were highlighted.

Temperature-dependence of beam-driven dynamics in graphene-fullerene sandwiches.

C60 fullerenes encapsulated between graphene sheets were investigated by aberration-corrected high-resolution transmission electron microscopy at different temperatures, namely about 93 K, 293 K and 733 K, and by molecular dynamics simulations. We studied beam-induced dynamics of the C60 fullerenes and the encapsulating graphene, measured the critical doses for the initial damage to the fullerenes and followed the beam-induced polymerization. We find that, while the doses for the initial damage do not strongly depend on temperature, the clusters formed by the subsequent polymerization are more tubular at lower temperatures, while sheet-like structures are generated at higher temperatures. The experimental findings are supported by the results of first-principles and analytical potential molecular dynamics simulations. The merging of curved carbon sheets is clearly promoted at higher temperatures and proceeds at once over few-nm segments.

Interrogation of 3d Transition Bimetallic Nanocrystal Nucleation and Growth Using In Situ Electron Microscope and Synchrotron X-ray Techniques.

Understanding the nucleation and growth mechanism of 3d transition bimetallic nanocrystals (NCs) is crucial to developing NCs with tailored nanostructures and properties. However, it remains a significant challenge due to the complexity of 3d bimetallic NCs formation and their sensitivity to oxygen. Here, by combining in situ electron microscopy and synchrotron X-ray techniques, we elucidate the nucleation and growth pathways of Fe-Ni NCs. Interestingly, the formation of Fe-Ni NCs emerges from the assimilation of Fe into Ni clusters together with the reduction of Fe-Ni oxides. Subsequently, these NCs undergo solid-state phase transitions, resulting in two distinct solid solutions, ultimately dominated by γ-Fe3Ni2. Furthermore, we deconvolve the interplays between local coordination and electronic state concerning the growth temperature. We directly visualize the oxidation-state distributions of Fe and Ni at the nanoscale and investigate their changes. This work may reshape and enhance the understanding of nucleation and growth in atomic crystallization.

Dimensional Scaling of Ferroelectric Properties of Hafnia-Zirconia Thin Films: Electrode Interface Effects.

Hafnia-based ferroelectric (FE) thin films are promising candidates for semiconductor memories. However, a fundamental challenge that persists is the lack of understanding regarding dimensional scaling, including thickness scaling and area scaling, of the functional properties and their heterogeneity in these films. In this work, excellent ferroelectricity and switching endurance are demonstrated in 4 nm-thick Hf0.5Zr0.5O2 (HZO) capacitors with molybdenum electrodes in capacitors as small as 65 nm × 45 nm in size. The HZO layer in these capacitors can be crystallized into the ferroelectric orthorhombic phase at the low temperature of 400 °C, making them compatible for back-end-of-line (BEOL) FE memories. With the benefits of thickness scaling, low operation voltage (1.2 V) is achieved with high endurance (>1010 cycles); however, a significant fatigue regime is noted. We observed that the bottom electrode, rather than the top electrode, plays a dominant role in the thickness scaling of HZO ferroelectric behavior. Furthermore, ultrahigh switched polarization (remanent polarization 2Pr ∼ 108 µC cm-2) is observed in some nanoscale devices. This study advances the understanding of dimensional scaling effects in HZO capacitors for high-performance FE memories.

Engineering Oxide Epitaxy beyond Substrate Constraint.

Orientation engineering is a crucial aspect of thin film growth, and it is rather challenging to engineer film epitaxy beyond the substrate constraint. Guided by density functional theory calculations, we use SrRuO3 (SRO) as a buffer layer and successfully deposit [111]-oriented CoFe2O4 (CFO) on [001]-, [110]-, and [111]-oriented SrTiO3 (STO) substrates. This enables subsequent growth of [111]-oriented functional oxides, such as PbTiO3 (PTO), overcoming the constraint of the substrate. This strategy is quite general and applicable to lanthanum aluminate and yttria-stabilized zirconia substrates as well. X-ray Φ scans and atomic resolution aberration-corrected scanning transmission electron microscopy (AC-STEM) reveal detailed epitaxial relations in each of the cases, with four variants of [111]-CFO found on [001]-STO and two variants found on [110]-STO, formed to mitigate the large lattice misfit strain between the film and substrate. Our strategy thus provides a general pathway for orientation engineering of oxide epitaxy beyond substrate constraint.

Bit by bit toward the diversity of metopids: Description of the genus Pidimetopus n. gen. (Ciliophora: Armophorea).

While metopids (Armophorea: Metopida) represent the most species-rich group of free-living anaerobic ciliates thriving in hypoxic environments, our understanding of their true diversity remains incomplete. Most metopid species are still characterized only morphologically. Particularly, the so-called IAC clade (named in the past after some of the taxa included, Idiometopus, Atopospira, and Clevelandellida), comprising free-living members as well as the endosymbiotic ones (order Clevelandellida), is in serious need of revision. In our study, we establish a new free-living genus in the IAC clade, Pidimetopus n. gen., with descriptions of two new species, P. nanus n. sp., and P. permonicus n. sp., using up-to-date molecular and morphologic methods. The genus is characterized by small cells (up to 75 µm long), not more than 10 adoral membranelles and eight somatic kineties, and usually, four long caudal cilia that can stiffen. In addition to morphologic and molecular characterizations, we also conducted a statistical morphotype analysis of the polymorphic species P. nanus n. sp. We discuss the relevance of the earlier morphologically described species Metopus minor as a putative collective taxon for several small metopids less than 50 µm long.

Quasi-operando Transmission Electron Microscopy Diagnostics for Electrocatalytic Processes in Liquids.

The need to relate the mechano-physico-chemical phenomena in liquid-based electrocatalysts to the stages of start-up, operation, and shut-down phases is one of the major challenges that the energy community is facing. Understanding these phenomena will pave the way for the tailor-made design of efficient, commercially viable electrocatalytic systems. Transmission electron microscopy plays an important role in the investigation of local electrocatalytic effects, complementing other operando characterization techniques. Herein, after attempting to define the meaning of operando methodologies in relation to electron microscopy studies, the progress in the field is reviewed in terms of the knowledge gained about the catalysts, the solid-liquid interfaces, and the solid-liquid-gas interfacial phenomena for several electrocatalytic reactions. Finally, the parameters that require consideration in operando ec-LPTEM studies of electrocatalytic systems are discussed.

Development and Fabrication of a Multi-Layer Planar Solar Light Absorber Achieving High Absorptivity and Ultra-Wideband Response from Visible Light to Infrared.

The objective of this study is to create a planar solar light absorber that exhibits exceptional absorption characteristics spanning from visible light to infrared across an ultra-wide spectral range. The eight layered structures of the absorber, from top to bottom, consisted of Al2O3, Ti, Al2O3, Ti, Al2O3, Ni, Al2O3, and Al. The COMSOL Multiphysics® simulation software (version 6.0) was utilized to construct the absorber model and perform simulation analyses. The first significant finding of this study is that as compared to absorbers featuring seven-layered structures (excluding the top Al2O3 layer) or using TiO2 or SiO2 layers as substituted for Al2O3 layer, the presence of the top Al2O3 layer demonstrated superior anti-reflection properties. Another noteworthy finding was that the top Al2O3 layer provided better impedance matching compared to scenarios where it was absent or replaced with TiO2 or SiO2 layers, enhancing the absorber's overall efficiency. Consequently, across the ultra-wideband spectrum spanning 350 to 1970 nm, the average absorptivity reached an impressive 96.76%. One significant novelty of this study was the utilization of various top-layer materials to assess the absorption and reflection spectra, along with the optical-impedance-matching properties of the designed absorber. Another notable contribution was the successful implementation of evaporation techniques for depositing and manufacturing this optimized absorber. A further innovation involved the use of transmission electron microscopy to observe the thickness of each deposition layer. Subsequently, the simulated and calculated absorption spectra of solar energy across the AM1.5 spectrum for both the designed and fabricated absorbers were compared, demonstrating a match between the measured and simulated results.

Isolation and Characterization of Extracellular Vesicles Derived from Ex Vivo Culture of Visceral Adipose Tissue.

Extracellular vesicles (EVs) are a heterogeneous group of nanoparticles possessing a lipid bilayer membrane that plays a significant role in intercellular communication by transferring their cargoes, consisting of peptides, proteins, fatty acids, DNA, and RNA, to receiver cells. Isolation of EVs is cumbersome and time-consuming due to their nano size and the co-isolation of small molecules along with EVs. This is why current protocols for the isolation of EVs are unable to provide high purity. So far, studies have focused on EVs derived from cell supernatants or body fluids but are associated with a number of limitations. Cell lines with a high passage number cannot be considered as representative of the original cell type, and EVs isolated from those can present distinct properties and characteristics. Additionally, cultured cells only have a single cell type and do not possess any cellular interactions with other types of cells, which normally exist in the tissue microenvironment. Therefore, studies involving the direct EVs isolation from whole tissues can provide a better understanding of intercellular communication in vivo. This underscores the critical need to standardize and optimize protocols for isolating and characterizing EVs from tissues. We have developed a differential centrifugation-based technique to isolate and characterize EVs from whole adipose tissue, which can be potentially applied to other types of tissues. This may help us to better understand the role of EVs in the tissue microenvironment in both diseased and normal conditions. Key features • Isolation of tissue-derived extracellular vesicles from ex vivo culture of visceral adipose tissue or any whole tissue. • Microscopic visualization of extracellular vesicles' morphology without dehydration steps, with minimum effect on their shape. • Flow cytometry approach to characterize the extracellular vesicles using specific protein markers, as an alternative to the time-consuming western blot.

New Poisson denoising method for pulse-count STEM imaging.

With the recent progress in the development of detectors in electron microscopy, it has become possible to directly count the number of electrons per pixel, even with a scintillator-type detector, by incorporating a pulse-counting module. To optimize a denoising method for electron counting imaging, in this study, we propose a Poisson denoising method for atomic-resolution scanning transmission electron microscopy images. Our method is based on the Markov random field model and Bayesian inference, and we can reduce the electron dose by a factor of about 15 times or further below. Moreover, we showed that the method of reconstruction from multiple images without integrating them performs better than that from an integrated image.

Angular momentum transfer from swift electrons to non-spherical nanoparticles within the dipolar approximation.

In this work, we study the angular momentum transfer from a single swift electron to non-spherical metallic nanoparticles, specifically investigating spheroidal and polyhedral (Platonic Solids) shapes. While previous research has predominantly focused on spherical nanoparticles, our work expands the knowledge by exploring various geometries. Employing classical electrodynamics and the small particle limit, we calculate the angular momentum transfer by integrating the spectral density, ensuring causality through Fourier-transform analysis. Our findings demonstrate that prolate spheroidal nanoparticles exhibit a single blueshifted plasmonic resonance, compared to spherical nanoparticles of equivalent volume, resulting in lower angular momentum transfer. Conversely, oblate nanoparticles display two resonances - one blueshifted and one redshifted - resulting in a higher angular momentum transfer than their spherical counterparts. Additionally, Platonic Solids with fewer faces exhibit significant redshifts in plasmonic resonances, leading to higher angular momentum transfer due to edge effects. We also observe resonances and angular momentum transfers with similar characteristics in specific pairs of Platonic Solids, known as duals. These results highlight promising applications, particularly in electron tweezers technology.

Chondroitin Sulfate-Based Nanocapsules as Nanocarriers for Drugs and Nutraceutical Supplements.

Oil-core nanocapsules (NCs, also known as nanoemulsions) are of great interest due to their application as efficient carriers of various lipophilic bioactives, such as drugs. Here, we reported for the first time the preparation and characterization of NCs consisting of chondroitin sulfate (CS)-based shells and liquid oil cores. For this purpose, two amphiphilic CS derivatives (AmCSs) were obtained by grafting the polysaccharide chain with octadecyl or oleyl groups. AmCS-based NCs were prepared by an ultrasound-assisted emulsification of an oil phase consisting of a mixture of triglyceride oil and vitamin E in a dispersion of AmCSs. Dynamic light scattering and cryo-transmission electron microscopy showed that the as-prepared core-shell NCs have typical diameters in the range of 30-250 nm and spherical morphology. Since CS is a strong polyanion, these particles have a very low surface potential, which promotes their stabilization. The cytotoxicity of the CS derivatives and CS-based NCs and their impact on cell proliferation were analyzed using human keratinocytes (HaCaTs) and primary human skin fibroblasts (HSFs). In vitro studies showed that AmCSs dispersed in an aqueous medium, exhibiting mild cytotoxicity against HaCaTs, while for HSFs, the harmful effect was observed only for the CS derivative with octadecyl side groups. However, the nanocapsules coated with AmCSs, especially those filled with vitamin E, show high biocompatibility with human skin cells. Due to their stability under physiological conditions, the high encapsulation efficiency of their hydrophobic compounds, and biocompatibility, AmCS-based NCs are promising carriers for the topical delivery of lipophilic bioactive compounds.

Cell Wall Microdomains in the External Glands of Utricularia dichotoma Traps.

The genus Utricularia (bladderworts) species are carnivorous plants that prey on invertebrates using traps with a high-speed suction mechanism. The outer trap surface is lined by dome-shaped glands responsible for secreting water in active traps. In terminal cells of these glands, the outer wall is differentiated into several layers, and even cell wall ingrowths are covered by new cell wall layers. Due to changes in the cell wall, these glands are excellent models for studying the specialization of cell walls (microdomains). The main aim of this study was to check if different cell wall layers have a different composition. Antibodies against arabinogalactan proteins (AGPs) were used, including JIM8, JIM13, JIM14, MAC207, and JIM4. The localization of the examined compounds was determined using immunohistochemistry techniques and immunogold labeling. Differences in composition were found between the primary cell wall and the cell secondary wall in terminal gland cells. The outermost layer of the cell wall of the terminal cell, which was cuticularized, was devoid of AGPs (JIM8, JIM14). In contrast, the secondary cell wall in terminal cells was rich in AGPs. AGPs localized with the JIM13, JIM8, and JIM14 epitopes occurred in wall ingrowths of pedestal cells. Our research supports the hypothesis of water secretion by the external glands.

Curved mineral platelets in bone.

Bone is a composite material principally made up of a mineral phase (apatite) and collagen fibrils. The mineral component of bone occurs in the form of polycrystalline platelets 2-6 nm in thickness. These platelets are packed and probably glued together in stacks of two or more, ranging up to >30 platelets. Here we show that most of these stacks are curved flat sheets whose cylindrical axes are oriented parallel to the long axes of collagen fibrils. Consequently, the curvature of the platelets is not detectable in TEM sections cut parallel to the collagen fibril axes. The radius of curvature around these axes ranges from about 25 nm (the average radius of the collagen fibrils) to 100's of nm. The shapes of these curved forms contribute to the compressive strength of bone. STATEMENT OF SIGNIFICANCE: Bone, the material of which bones are made, is mainly composed of a protein, collagen, and the mineral apatite (calcium phosphate). The crystals have long been known to be flat plates about 5 nanometers (nm) thick. Here we show that the crystals are bound together in curved platelets with a radius of curvature between 25 and several hundred nm, which weave between fibrils of collagen. Some platelets wrap tightly around fibrils. The platelets form stacks of from two to up to 30. The crystals in the platelets are all oriented parallel to the cylindrical fibrils even though most crystals are not in contact with collagen. These curved structures provide greater strength to bone.

Interface Design beyond Epitaxy: Oxide Heterostructures Comprising Symmetry-Forbidden Interfaces.

Epitaxial growth of thin-film heterostructures is generally considered the most successful procedure to obtain interfaces of excellent structural and electronic quality between 3D materials. However, these interfaces can only join material systems with crystal lattices of matching symmetries and lattice constants. This article presents a novel category of interfaces, the fabrication of which is membrane-based and does not require epitaxial growth. These interfaces therefore overcome the limitations imposed by epitaxy. Leveraging the additional degrees of freedom gained, atomically clean interfaces are demonstrated between threefold symmetric sapphire and fourfold symmetric SrTiO3. Atomic-resolution imaging reveals structurally well-defined interfaces with a novel moiré-type reconstruction.

High-Entropy Transition Metal Phosphorus Trichalcogenides for Rapid Sodium Ion Diffusion.

High-entropy strategies are regarded as a powerful means to enhance performance in energy storage fields. The improved properties are invariably ascribed to entropy stabilization or synergistic cocktail effect. Therefore, the manifested properties in such multicomponent materials are usually unpredictable. Elucidating the precise correlations between atomic structures and properties remains a challenge in high-entropy materials (HEMs). Herein, atomic-resolution scanning transmission electron microscopy annular dark field (STEM-ADF) imaging and four dimensions (4D)-STEM are combined to directly visualize atomic-scale structural and electric information in high-entropy FeMnNiVZnPS3. Aperiodic stacking is found in FeMnNiVZnPS3 accompanied by high-density strain soliton boundaries (SSBs). Theoretical calculation suggests that the formation of such structures is attributed to the imbalanced stress of distinct metal-sulfur bonds in FeMnNiVZnPS3. Interestingly, the electric field concentrates along the two sides of SSBs and gradually diminishes toward the two-dimensional (2D) plane to generate a unique electric field gradient, strongly promoting the ion-diffusion rate. Accordingly, high-entropy FeMnNiVZnPS3 demonstrates superior ion-diffusion coefficients of 10-9.7-10-8.3 cm2 s-1 and high-rate performance (311.5 mAh g-1 at 30 A g-1). This work provides an alternative way for the atomic-scale understanding and design of sophisticated HEMs, paving the way for property engineering in multi-component materials.