Visualization of the Final Stage of Sintering in Nanoceramics with Atomic Resolution.

The deep understanding of the sintering mechanism is pivotal to optimizing denser ceramics production. Although several models explain the sintering satisfactorily on the micrometric scale, the extrapolation for nanostructured systems is not trivial. Aiming to provide additional information about the particularities of the sintering at the nanoscale, we performed in situ experiments using high-resolution transmission electron microscopy (HRTEM). We studied the pore elimination process in a ZrO2 thin film and identified a high anisotropic pore elimination. Interestingly, there is a redistribution of the atoms from the rough surface in the solid-gas surface, followed by the atom attachment in a faceted surface. Finally, we found evidence of the pore acting as a pin, reducing the GB mobility. These findings certainly can contribute to enhance the kinetic models to describe the densification process of systems at the nanoscale.

Stability and Rupture of an Ultrathin Ionic Wire.

Using a combination of in situ high-resolution transmission electron microscopy and density functional theory, we report the formation and rupture of ZrO_{2} atomic ionic wires. Near rupture, under tensile stress, the system favors the spontaneous formation of oxygen vacancies, a critical step in the formation of the monatomic bridge. In this length scale, vacancies provide ductilelike behavior, an unexpected mechanical behavior for ionic systems. Our results add an ionic compound to the very selective list of materials that can form monatomic wires and they contribute to the fundamental understanding of the mechanical properties of ceramic materials at the nanoscale.

Manganese silicide nanowires via metallic flux nanonucleation: growth mechanism and temperature-dependent resistivity.

Mn5Si3nanowires are believed to be the building blocks of the newest trends of flexible and stretchable devices in nanoelectronics. In this context , growing Mn5Si3nanowires, as well as characterizing their electronic transport properties provide insight into their phenomenology. In this work, we report on the growth mechanism of Mn5Si3nanowires produced by the metallic flux nanonucleation method, as well as the resistivity measurements of these nanostructures. Our calculation allows us, by using the Washburn equation for pore infiltration, to give a guess on why we obtain Mn-rich nanowires. In addition, some morphological aspects of the diameter-modulated Mn5Si3nanowires were discussed based on the classical nucleation theory. From the resistivity measurements for the smallest diameter among the nanowires, we observed a significant reduction of around 37% of the phonons characteristic temperature by fitting the Bloch-Grünesein formula with other sources of scattering. Our results lead to a better understanding on the recent metallic flux nanonucleation growth method, as well as going a step further into the electronic transport properties of the Mn5Si3nanowires.

Inside the Protein Corona: From Binding Parameters to Unstained Hard and Soft Coronas Visualization.

Proteins spontaneously adsorb on nanoparticle surfaces when injected into the bloodstream. It drastically modifies the nanoparticle's fate and how they interact with organs and cells. Although this protein layer (protein corona) has been widely studied, the robustness of the most employed characterization methods and the visualization of its unstained fractions remain open questions. Here, synchrotron-based small-angle X-ray scattering was used to follow the corona formation and estimate binding parameters. At the same time, transmission electron microscopy under cryogenic conditions associated with cross-correlation image processing and energy-filtered transmission electron microscopy allowed to determine protein corona morphology and thickness together with the visualization of its unstained hard and soft fractions. The above-presented strategy shows tremendous potential for deciphering fundamental protein corona aspects and can contribute to rational medical nanoparticle engineering.

Tailoring Pseudo-Zwitterionic Bifunctionalized Silica Nanoparticles: From Colloidal Stability to Biological Interactions.

Zwitterionic molecules are known to resist nonspecific protein adsorption and have been proposed as an alternative to the widely used polyethylene glycol. Recently, zwitterionic-like nanoparticles were created from the coimmobilization of positive and negative ligands, resulting in surfaces that also prevent protein corona formation while keeping available sites for bioconjugation. However, it is unclear if they are able to keep their original properties when immersed in biological environments while retaining a toxicity-free profile, indispensable features before considering these structures for clinics. Herein, we obtained optimized zwitterionic-like silica nanoparticles from the functionalization with varying ratios of THPMP and DETAPTMS organosilanes and investigated their behavior in realistic biological milieu. The generated zwitterionic-like particle was able to resist single-protein adsorption, while the interaction with a myriad of serum proteins led to significant loss of colloidal stability. Moreover, the zwitterionic particles presented poor hemocompatibility, causing considerable disruption of red blood cells. Our findings suggest that the exposure of ionic groups allows these structures to directly engage with the environment and that electrostatic neutrality is not enough to grant low-fouling and stealth properties.

Microwave-Driven Hexagonal-to-Monoclinic Transition in BiPO4: An In-Depth Experimental Investigation and First-Principles Study.

Present theoretical and experimental work provides an in-depth understanding of the morphological, structural, electronic, and optical properties of hexagonal and monoclinic polymorphs of bismuth phosphate (BiPO4). Herein, we demonstrate how microwave irradiation induces the transformation of a hexagonal phase to a monoclinic phase in a short period of time and, thus, the photocatalytic performance of BiPO4. To complement and rationalize the experimental results, first-principles calculations have been performed within the framework of density functional theory. This was aimed at obtaining the geometric, energetic, and structural parameters as well as vibrational frequencies; further, the electronic properties (band structure diagram and density of states) of the bulk and corresponding surfaces of both the hexagonal and monoclinic phases of BiPO4 were also acquired. A detailed characterization of the low vibrational modes of both the hexagonal and monoclinic polymorphs is key to explaining the irreversible phase transformation from hexagonal to monoclinic. On the basis of the calculated values of the surface energies, a map of the available morphologies of both phases was obtained by using Wulff construction and compared to the observed scanning electron microscopy images. The BiPO4 crystals obtained after 16-32 min of microwave irradiation provided excellent photodegradation of Rhodamine B under visible-light irradiation. This enhancement was found to be related to the surface energy and the types of clusters formed on the exposed surfaces of the morphology. These findings provide details of the hexagonal-to-monoclinic phase transition in BiPO4 during microwave irradiation; further, the results will assist in the design of electronic devices with higher efficiency and reliability.

The origin and evolution of human glutaminases and their atypical C-terminal ankyrin repeats.

On the basis of tissue-specific enzyme activity and inhibition by catalytic products, Hans Krebs first demonstrated the existence of multiple glutaminases in mammals. Currently, two human genes are known to encode at least four glutaminase isoforms. However, the phylogeny of these medically relevant enzymes remains unclear, prompting us to investigate their origin and evolution. Using prokaryotic and eukaryotic glutaminase sequences, we built a phylogenetic tree whose topology suggested that the multidomain architecture was inherited from bacterial ancestors, probably simultaneously with the hosting of the proto-mitochondrion endosymbiont. We propose an evolutionary model wherein the appearance of the most active enzyme isoform, glutaminase C (GAC), which is expressed in many cancers, was a late retrotransposition event that occurred in fishes from the Chondrichthyes class. The ankyrin (ANK) repeats in the glutaminases were acquired early in their evolution. To obtain information on ANK folding, we solved two high-resolution structures of the ANK repeat-containing C termini of both kidney-type glutaminase (KGA) and GLS2 isoforms (glutaminase B and liver-type glutaminase). We found that the glutaminase ANK repeats form unique intramolecular contacts through two highly conserved motifs; curiously, this arrangement occludes a region usually involved in ANK-mediated protein-protein interactions. We also solved the crystal structure of full-length KGA and present a small-angle X-ray scattering model for full-length GLS2. These structures explain these proteins' compromised ability to assemble into catalytically active supra-tetrameric filaments, as previously shown for GAC. Collectively, these results provide information about glutaminases that may aid in the design of isoform-specific glutaminase inhibitors.

Exploring Au Droplet Motion in Nanowire Growth: A Simple Route toward Asymmetric GaP Morphologies.

Here we show a new nanowire growth procedure, exploring the thermally activated motion of Au droplets on III-V surfaces. We show that by setting a single growth parameter we can activate the crawling motion of Au droplets in vacuum and locally modify surface composition in order to enhance vapor-solid (VS) growth along oxide-free areas on the trail of the metal particle. Asymmetric VS growth rates are comparable in magnitude to the vapor-liquid-solid growth, producing unconventional wurtzite GaP morphologies, which shows negligible defect density as well as optical signal in the green spectral region. Finally, we demonstrate that this effect can also be explored in different substrate compositions and orientations with the final shape finely tuned by group III flow and nanoparticle size. This distinct morphology for wurtzite GaP nanomaterials can be interesting for the design of nanophotonics devices.

Influence of Inert and Oxidizing Atmospheres on the Physical and Optical Properties of Luminescent Carbon Dots Prepared through Pyrolysis of a Model Molecule.

This work used L-tartaric acid as a model molecule to evaluate how the use of inert and oxidizing atmospheres during pyrolysis affected the physical and optical properties of the resulting carbon dots (CDs). Pyrolysis revealed to be a simple procedure that afforded CDs in a single step, dismissed the addition of organic solvents, and involved only one extraction stage that employed water. By X-ray diffraction a dependency between the structure of the CDs and the atmosphere (oxidizing or inert) used during the pyrolysis was found. Potentiometric titration demonstrated that the CDs were largely soluble in water; it also aided characterization of the various groups that contained sp(3) -hybridized carbon atoms on the surface of the dots. Raman spectroscopy suggested that different amounts of sp(2)- and sp(3)-hybridized carbon atoms emerged on the CDs depending on the pyrolysis atmosphere. In conclusion, the pyrolysis atmosphere influenced the physical properties, such as the composition and the final structure.

Functionalized Silica Nanoparticles As an Alternative Platform for Targeted Drug-Delivery of Water Insoluble Drugs.

The selective action of drugs in tumor cells is a major problem in cancer therapy. Most chemotherapy drugs act nonspecifically and damage both cancer and healthy cells causing various side effects. In this study, the preparation of a selective drug delivery system, which is able to act as a carrier for hydrophobic and anticancer drugs is reported. Amino-functionalized silica nanoparticles loaded with curcumin were successfully synthesized via sol-gel approach and duly characterized. Thereafter, the targeting ligand, folate, was covalently attached to amino groups of nanoparticle surface through amide bond formation. The cytotoxic effect of nanoparticles on prostate cancer cells line was evaluated and compared to normal cells line (prostate epithelial cell). Cytotoxicity experiments demonstrated that folate-functionalized nanoparticles were significantly cytotoxic to tumor cells, whereas normal cells were much less affected by the presence of these structures.

Understanding the fundamental electrical and photoelectrochemical behavior of a hematite photoanode.

Hematite is considered to be the most promising material used as a photoanode for water splitting and here we utilized a sintered hematite photoanode to address the fundamental electrical, electrochemical and photoelectrochemical behavior of this semiconductor oxide. The results presented here allowed us to conclude that the addition of Sn(4+) decreases the grain boundary resistance of the hematite polycrystalline electrode. Heat treatment in a nitrogen (N2) atmosphere also contributes to a decrease of the grain boundary resistance, supporting the evidence that the presence of oxygen is fundamental for the formation of a voltage barrier at the hematite grain boundary. The N2 atmosphere affected both doped and undoped sintered electrodes. We also observed that the heat treatment atmosphere modifies the surface states of the solid-liquid interface, changing the charge-transfer resistance. A two-step treatment, with the second being performed at a low temperature in an oxygen (O2) atmosphere, resulted in a better solid-liquid interface.

Active glutaminase C self-assembles into a supratetrameric oligomer that can be disrupted by an allosteric inhibitor.

The phosphate-dependent transition between enzymatically inert dimers into catalytically capable tetramers has long been the accepted mechanism for the glutaminase activation. Here, we demonstrate that activated glutaminase C (GAC) self-assembles into a helical, fiber-like double-stranded oligomer and propose a molecular model consisting of seven tetramer copies per turn per strand interacting via the N-terminal domains. The loop (321)LRFNKL(326) is projected as the major regulating element for self-assembly and enzyme activation. Furthermore, the previously identified in vivo lysine acetylation (Lys(311) in humans, Lys(316) in mouse) is here proposed as an important down-regulator of superoligomer assembly and protein activation. Bis-2-(5-phenylacetamido-1,3,4-thiadiazol-2-yl)ethyl sulfide, a known glutaminase inhibitor, completely disrupted the higher order oligomer, explaining its allosteric mechanism of inhibition via tetramer stabilization. A direct correlation between the tendency to self-assemble and the activity levels of the three mammalian glutaminase isozymes was established, with GAC being the most active enzyme while forming the longest structures. Lastly, the ectopic expression of a fiber-prone superactive GAC mutant in MDA-MB 231 cancer cells provided considerable proliferative advantages to transformed cells. These findings yield unique implications for the development of GAC-oriented therapeutics targeting tumor metabolism.

Acid selenites as new selenium precursor for CdSe quantum dot synthesis.

Chemical precursors for nanomaterials synthesis have become essential to tune particle size, composition, morphology, and unique properties. New inexpensive precursors investigation that precisely controls these characteristics is highly relevant. We studied new Se precursors, the acid selenites (R-O-SeOOH), to synthesize CdSe quantum dots (QDs). They were produced at room temperature by the Image 1 reaction with alcohols having different alkyl chains and were characterized by 1H NMR confirming their structures. This unprecedented precursor generates high-quality CdSe nanocrystals with narrow size distribution in the zinc-blend structure showing controlled optical properties. Advanced characterization detailed the CdSe structure showing stacking fault defects and its dependence on the used R-O-SeOOH. The QDs formation was examined using a time-dependent growth kinetics model. Differences in the nanoparticle surface structure influenced the optical properties, and they were correlated to the Se-precursor nature. Small alkyl chain acid selenites generally lead to more controlled QDs morphology, while the bigger alkyl chain leads to slightly upper quantum yields. Acid selenites can potentially replace Se-precursors at competitive costs in the metallic chalcogenide nanoparticles. Image 1 is chemically stable, and alcohols are cheap and less toxic than the reactants used today, making acid selenites a more sustainable Se precursor.

Tuning the Chemical and Electrochemical Properties of Paper-Based Carbon Electrodes by Pyrolysis of Polydopamine.

Electrochemical paper-based analytical devices represent an important platform for portable, low-cost, affordable, and decentralized diagnostics. For this kind of application, chemical functionalization plays a pivotal role to ensure high clinical performance by tuning surface properties and the area of electrodes. However, controlling different surface properties of electrodes by using a single functionalization route is still challenging. In this work, we attempted to tune the wettability, chemical composition, and electroactive area of carbon-paper-based devices by thermally treating polydopamine (PDA) at different temperatures. PDA films were deposited onto pyrolyzed paper (PP) electrodes and thermally treated in the range of 300-1000 °C. After deposition of PDA, the surface is rich in nitrogen and oxygen, it is superhydrophilic, and it has a high electroactive area. As the temperature increases, the surface becomes hydrophobic, and the electroactive area decreases. The surface modifications were followed by Raman, X-ray photoelectron microscopy (XPS), laser scanning confocal microscopy (LSCM), contact angle, scanning electron microscopy (SEM-EDS), electrical measurements, transmission electron microscopy (TEM), and electrochemical experiments. In addition, the chemical composition of nitrogen species can be tuned on the surface. As a proof of concept, we employed PDA-treated surfaces to anchor [AuCl4]- ions. After electrochemical reduction, we observed that it is possible to control the size of the nanoparticles on the surface. Our route opens a new avenue to add versatility to electrochemical interfaces in the field of paper-based electrochemical biosensors.

Probing the cw-Laser-Induced Fluorescence Enhancement in CsPbBr3 Nanocrystal Thin Films: An Interplay between Photo and Thermal Activation.

Perovskite nanocrystals hold significant promise for a wide range of applications, including solar cells, LEDs, photocatalysts, humidity and temperature sensors, memory devices, and low-cost photodetectors. Such technological potential stems from their exceptional quantum efficiency and charge carrier conduction capability. Nevertheless, the underlying mechanisms of photoexcitation, such as phase segregation, annealing, and ionic diffusion, remain insufficiently understood. In this context, we harnessed hyperspectral fluorescence microspectroscopy to advance our comprehension of fluorescence enhancement triggered by UV continuous-wave (cw) laser irradiation of CsPbBr3 colloidal nanocrystal thin films. Initially, we explored the kinetics of fluorescence enhancement and observed that its efficiency (φph) correlates with the laser power (P), following the relationship φph = 7.7⟨P⟩0.47±0.02. Subsequently, we estimated the local temperature induced by the laser, utilizing the finite-difference method framework, and calculated the activation energy (Ea) required for fluorescence enhancement to occur. Our findings revealed a very low activation energy, Ea ∼ 9 kJ/mol. Moreover, we mapped the fluorescence photoenhancement by spatial scanning and real-time static mode to determine its microscale length. Below a laser power of 60 µW, the photothermal diffusion length exhibited nearly constant values of approximately (22 ± 5) µm, while a significant increase was observed at higher laser power levels. These results were ascribed to the formation of nanocrystal superclusters within the film, which involves the interparticle spacing reduction, creating the so-called quantum dot solid configuration along with laser-induced annealing for higher laser powers.

Tuning resistive switching on single-pulse doped multilayer memristors.

Short-period multilayers containing ultrathin atomic layers of Al embedded in titanium dioxide (TiO(2)) film-here called single-pulse doped multilayers-are fabricated by atomic layer deposition (ALD) growth methods. The approach explored here is to use Al atoms through single-pulsed deposition to locally modify the chemical environment of TiO(2) films, establishing a chemical control over the resistive switching properties of metal/oxide/metal devices. We show that this simple methodology can be employed to produce well-defined and controlled electrical characteristics on oxide thin films without compound segregation. The increase in volume of the embedded Al(2)O(3) plays a crucial role in tuning the conductance of devices, as well as the switching bias. The stacking of these oxide compounds and their use in electrical devices is investigated with respect to possible crystalline phases and local compound formation via chemical recombination. It is shown that our method can be used to produce compounds that cannot be synthesized a priori by direct ALD growth procedures but are of interest due to specific properties such as thermal or chemical stability, electrical resistivity or electric field polarization possibilities. The monolayer doping discussed here impacts considerably on the broadening of the spectrum of performance and technological applications of ALD-based memristors, allowing for additional degrees of freedom in the engineering of oxide devices.

Flowing through Gastrointestinal Barriers with Model Nanoparticles: From Complex Fluids to Model Human Intestinal Epithelium Permeation.

Most nanomaterial-based medicines are intravenously applied since oral administration comprises challenging-related biological obstacles, such as interactions with distinct digestive fluids and their transport through the intestinal barrier. Moreover, there is a lack of nanoparticle-based studies that faithfully consider the above-cited obstacles and boost oral-administered nanomedicines' rational design. In this study, the physicochemical stability of fluorescent model silica nanoparticles (f-SiO2NPs) passing through all simulated gastrointestinal fluids (salivary, gastric, and intestinal) and their absorption and transport across a model human intestinal epithelium barrier are investigated. An aggregation/disaggregation f-SiO2NPs process is identified, although these particles remain chemically and physically stable after exposure to digestive fluids. Further, fine imaging of f-SiO2NPs through the absorption and transport across the human intestinal epithelium indicates that nanoparticle transport is time-dependent. The above-presented protocol shows tremendous potential for deciphering fundamental gastrointestinal nanoparticles' evolution and can contribute to rational oral administration-based nanomedicine design.

Self-Diffusion versus Intentional Doping: Beneficial and Damaging Impact on Hematite Photoanode Interfaces.

The comprehension of side effects caused by high-temperature thermal treatments in the design of (photo)electrodes is essential to achieve efficient and cost-effective devices for solar water splitting. This investigation explores the beneficial and damaging impacts of thermal treatments in the (photo)electrode design, unraveling the impact of self-diffusion and its consequences. The industrial-friendly polymeric precursor synthesis (PPS) method, which is known for its easy technological application, was chosen as the fabrication technique for hematite photoabsorbers. For substrate evaluation, two types of conductive glass substrates, aluminum borosilicate and quartz, both coated with fluorine-doped tin oxide (ABS/FTO and QTZ/FTO, respectively), were subjected to thermal treatments following the PPS protocol. Optical and structural analyses showed no significant alterations in substrate properties, whereas X-ray photoelectron spectroscopy (XPS) revealed the migration of silicon and calcium ions from the glass component to the FTO surface. This diffusion can be further mitigated by an oxide buffer layer. To track the potential ion diffusion on the photoabsorber surface and assess its effect on the photoelectrode performance, hematite was selected as the model material and deposited onto the glass substrates. From all the ions that could possibly migrate, only Si4+ and Ca2+ originating from the glass component, as well as Sn4+ from the fluorine-doped tin oxide (FTO), were detected on the surface of the hematite photoabsorber. Interestingly, the so-called "self-diffusion" of these ions did not result in any beneficial effect on the hematite photoelectrochemical response. Instead, intentional modifications showed more substantial impacts on the photoelectrochemical efficiency compared to unintentional self-diffusion. Therefore, "self-diffusion", which can unintentionally dope the hematite, is not sufficient to significantly impact the final photocurrent. These findings emphasize the importance of understanding the true effect of thermal treatments on the photoelectrode properties to unlock their full potential in photoelectrochemical applications.

Background optimization of powder electron diffraction for implementation of the e-PDF technique and study of the local structure of iron oxide nanocrystals.

The local structural characterization of iron oxide nanoparticles is explored using a total scattering analysis method known as pair distribution function (PDF) (also known as reduced density function) analysis. The PDF profiles are derived from background-corrected powder electron diffraction patterns (the e-PDF technique). Due to the strong Coulombic interaction between the electron beam and the sample, electron diffraction generally leads to multiple scattering, causing redistribution of intensities towards higher scattering angles and an increased background in the diffraction profile. In addition to this, the electron-specimen interaction gives rise to an undesirable inelastic scattering signal that contributes primarily to the background. The present work demonstrates the efficacy of a pre-treatment of the underlying complex background function, which is a combination of both incoherent multiple and inelastic scatterings that cannot be identical for different electron beam energies. Therefore, two different background subtraction approaches are proposed for the electron diffraction patterns acquired at 80 kV and 300 kV beam energies. From the least-square refinement (small-box modelling), both approaches are found to be very promising, leading to a successful implementation of the e-PDF technique to study the local structure of the considered nanomaterial.

Scalable and green formation of graphitic nanolayers produces highly conductive pyrolyzed paper toward sensitive electrochemical sensors.

While pyrolyzed paper (PP) is a green and abundant material that can provide functionalized electrodes with wide detection windows for a plethora of targets, it poses long-standing challenges against sensing assays such as poor electrical conductivity, with resistivities generally higher than 200.0 mΩ cm (e.g., gold and silver show resistivities 1000-fold lower, ∼0.2 mΩ cm). In this regard, the fundamental hypothesis that drives this work is whether a scalable, cost-effective, and eco-friendly strategy is capable of significantly reducing the resistivity of PP electrodes toward the development of sensitive electrochemical sensors, whether faradaic or capacitive. We address this hypothesis by simply annealing PP under an isopropanol atmosphere for 1 h, reaching resistivities as low as 7 mΩ cm. Specifically, the annealing of PP at 800 or 1000 °C under isopropanol vapor leads to the formation of a highly graphitic nanolayer (∼15 nm) on the PP surface, boosting conductivity as the delocalization of π electrons stemming from carbon sp2 is favored. The reduction of carbonyl groups and the deposition of dehydrated isopropanol during the annealing process are hypothesized herein as the dominant PP graphitization mechanisms. Electrochemical analyses demonstrated the capability of the annealed PP to increase the charge-transfer kinetics, with the optimum heterogeneous standard rate constant being roughly 3.6 × 10-3 cm s-1. This value is larger than the constants reported for other carbon electrodes and indium tin oxide. Furthermore, freestanding fingers of the annealed PP were prototyped using a knife plotter to fabricate impedimetric on-leaf electrodes. These wearable sensors ensured the real-time and in situ monitoring of the loss of water content from soy leaves, outperforming non-annealed electrodes in terms of reproducibility and sensitivity. Such an application is of pivotal importance for precision agriculture and development of agricultural inputs. This work addresses the foundations for the achievement of conductive PP in a scalable, low-cost, simple, and eco-friendly way, i.e. without producing any liquid chemical waste, providing new opportunities to translate PP-based sensitive electrochemical devices into practical use.