Amorphous Particles Research Articles

Mechanochemical Solid-State Immobilization of Photofunctional Dyes on Amorphous Silica Particles and Investigation of Their Interactive Mechanisms.

Amorphous silica particles (ASPs) have been reported to exhibit bioactive properties and are becoming the focus of attention as bioceramics. However, their interactions with proteins in living organisms remain to be understood and need to be investigated in order to achieve wider applications. Our research group found that chlorine (Cl)-containing ASPs are useful for protein immobilization. Photofunctional dyes (fluorescein (FS-), methylene blue (MB+)) that have the carboxy and amino groups as the main functional groups were immobilized on the Cl-containing ASPs via the mechanochemical method as the model molecule and their spectral properties were used to investigate and discuss the organic/inorganic interfacial bonding states. In FS-, the oxygen atoms of the carboxy groups in the molecule were immobilized by the hydrogen bonds with the silanol groups on the ASPs surfaces, indicating that there is an optimum Cl content for the immobilization as the monomer state. In the case of MB+, as the Cl concentration in the ASPs increases, the immobilization via the electrostatic interactions between the Cl in the ASPs and the terminal dimethylamino group, and the hydrogen bonding between the N atoms of the MB+ hetero ring and the particle silanol group were enhanced. These results mainly suggest that the protein adsorption system occurs through the hydrogen bonding between the carboxy groups of the protein and the silanol groups on the particles and via electrostatic interactions between the amino groups of the protein and the dissociated silanol groups and the contained Cl at the particles. Thus, the spectral characterization using dyes as probes is expected to predict the protein interactions with the amorphous silica particles.

Enhancement in Dissolution Profile of Cilnidipine by Nanonization Technique: Optimization by Box-Behnken design

Objectives: Cilnidipine has limited 25-30% of bioavailability due to BCS class II category drug. The aim of present work was to improve the solubility followed by dissolution rate of cilnidipine by formulation of nanosuspension. Materials and Methods: The nanosuspensionwas developed usingnanoprecipitation techniqueaidingultra-sonication with solvent (Dimethyl sulfoxide), antisolvent (water) and stabilizer (polyvinyl alcohol). The nano formulation was statistically optimized using Design Expert software by theBox-Behnken design. The concentration of Poly Vinyl Alcohol, Volume of Antisolvent and Stirring Time were considered as independent factors whereas Particle size and polydispersity index were considered as dependent factors. Results: The particle size of nanosuspension was found 178.57nm with narrow polydispersity index of 0.130. The microscopy study confirmed amorphous nature particles with rough surface. The zeta potential of 4.55 ±2.78 for optimized formulation finds stability of formulation during storage. The differential scanning calorimetry study and X-ray diffraction pattern showed the crystalline cilnidipine drug was converted to amorphous form upon precipitation into nanoparticles. Due to the nanonization of cilnidipine, the dissolution profile was noted as 92.41±3.56% which was significantly improved as compared with plain drug release data. The stability data showed satisfactory result for 2 months. Conclusion: It is summarized that the nanoprecipitation technique with ultra-sonication is approaching method for the formulation of homogenous nanosuspension with uniform sized dispersion of cilnidipine. Therefore, it can be assumed that the upon the enhancement in dissolution rate, the cilnidipine loaded nanosuspension may lead to improved absorption of drug from intestine followed by significant improvement in bioavailability.

Control of Biological Surface States on Chlorine-Doped Amorphous Silica Particles and Their Effective Absorptive Ability for Antibody Protein.

Amorphous silica particles (ASPs) have low biotoxicity and are used in foodstuffs; however, the adsorption states of proteins on their surfaces have not yet been clarified. If the adsorption states can be clarified and controlled, then a wide range of biological and medical applications can be expected. The conventional amorphous silica particles have the problem of protein adsorption due to the strong interaction with their dense silanol groups and denaturation. In this study, the surfaces of amorphous silica particles with a lower silanol group density were modified with a small amount of chlorine during the synthesis process to form a specific surface layer by adsorbing water molecules and ions in the biological fluid, thereby controlling the protein adsorption state. Specifically, the hydration state on the surface of the amorphous silica particles containing trace amounts of chlorine was evaluated, and the surface layer (especially the hydration state) for the adsorption of antibody proteins while maintaining their steric structures was evaluated and discussed. The results showed that the inclusion of trace amounts of chlorine increased the silanol groups and Si-Cl bonds in the topmost surface layer of the particles, thereby inducing the adsorption of ions and water molecules in the biological fluid. Then, it was found that a novel surface layer was formed by the effective adsorption of Na and phosphate ions, which would change the proportion of the components in the hydration layer. In particular, the proportion of the free water component increased by 21% with the doping of chlorine. Antibody proteins were effectively adsorbed on the particles doped with trace amounts of chlorine, and their steric adsorption states were evaluated. It was found that the proteins were clearly adsorbed and maintained the steric state of their secondary structure. In the immunoreactivity tests using streptavidin and biotin, biotin bound to the chlorine-doped particles showed efficient reactivity. In conclusion, this study is the first to discover the surface layer of the amorphous silica particles to maintain the steric structures of adsorbed proteins, which is expected to be used as a carrier particle for antibody test kits and immunochromatography.

Raman Characterization of Plastics: A DFT Study of Polystyrene.

Plastic materials are ubiquitous and raise concerns about their impact on health and the environment. To address these concerns, it is crucial to characterize the structural, size, and textural properties of plastics throughout their lifecycle from production to degradation. Raman spectroscopy appears as a valuable tool for this purpose, offering speed, robustness, and sensitivity to nanoscale and amorphous particles. In order to be properly used for plastics, the Raman response of reference materials needs to be carefully assessed, with the literature on such assessments being scarce. This study addresses this gap by using theoretical calculations to generate ab initio spectra for polystyrene, a reference material. The aim is to explain the origins of the spectral peaks and their consistency across various compositions and structures using linear ordered polymeric and finite amorphous models. The CRYSTAL package is employed to obtain full Raman spectra based on a careful benchmark of computational settings. While some peaks are present across all spectra and can serve for calibration, others exhibit structure-dependent behavior, enabling polymer identification. We conclude that Raman spectroscopy is a well-suited technique for plastics characterization provided that a careful analysis of signal origin is conducted to fully interpret the spectra and deploy applications.

Efficacy of Ga3+ ions on structural, biological and antimicrobial activity of mesoporous lithium silicate bioactive glasses for tissue engineering

Mesoporous bioactive glass nanoparticles (MBGNPs) containing therapeutic ions have shown significant promise in the realm of hard and soft tissue repair and regeneration, owing to their multifunctional biological properties. In this study, gallium-incorporated silica-based gallium incorporated MBGNPs (Ga-MBGNPs) with fixed amount of Li2O (8 mol %) were synthesized using an emulsion-assisted sol-gel method. The impact of Ga2O3 integration into the silicate glass network was evaluated by investigating the microtextural properties. The results confirmed the production of spherical-shaped, nano-sized, amorphous particles with an enhanced specific surface area and ordered hexagonal meso-porosity (10–20 nm) in the developed Ga-MBGNPs. The in vitro bioactivity, assessed through hydroxyapatite (HAp) layer formation in simulated body fluid (SBF), over varying time intervals (0, 1, 3, 7, 14 & 21 days), revealed pronounced formation of short rod-like carbonated HAp with increasing immersion time and Ga3+ content in all glasses. However, a delayed apatite formation was observed for composition-dependent Ga-4 and Ga-5 MBGs during the initial incubation periods (1, 3, and 7 days). Further, the presence of Li + ions along with Ga3+ enhanced the apatite deposition when compared with the only Ga3+ inclusion. Evaluation of degradation rate and pH values indicated enhanced apatite formation with lower Ga ion content, while a slight reduction was noted with higher Ga ion content, attributable to the presence of reactive Si–O–Si bonds. Furthermore, analysis using a Zeta potential analyzer confirmed the dispersibility and bioreactivity of all glass powders owing to their higher negative surface charge. Moreover, Ga-MBGNPs exhibited notable antimicrobial effects against both E. coli and S. aureus bacteria due to the release of Ga3+ ions. Overall, the findings suggest that the incorporation of Ga in MBGNPs renders them potential multifunctional candidates for expediting the healing of bone tissue injuries in biomedical applications.

Radical electron-induced cellulose-semiconductors

Bio-semiconductors are expected to be similar to organic semiconductors; however, they have not been utilized in application yet. In this study, we show the origin of electron appearance, N- and S-type negative resistances, rectification, and switching effects of semiconductors with energy storage capacities of up to 418.5 mJ/m2 using granulated amorphous kenaf cellulose particles (AKCPs). The radical electrons in AKCP at 295 K appear in cellulose via the glycosidic bond C1–O1·–C4. Hall effect measurements indicate an n–type semiconductor with a carrier concentration of 9.89 × 1015/cm3, which corresponds to a mobility of 10.66 cm2/Vs and an electric resistivity of 9.80 × 102 Ωcm at 298 K. The conduction mechanism in the kenaf tissue was modelled from AC impedance curves. The light and flexible cellulose-semiconductors may open up new avenues in soft electronics such as switching effect devices and bio-sensors, primarily because they are composed of renewable natural compounds.

Atomic-Scale Insights into Flow-Accelerated Corrosion of Carbon Steel

The role of flow velocity on the formation and dissolution of oxides on SA106Gr.B carbon steel was investigated at both microscopic and atomic scales. In static water, a compact oxide layer with highly faceted magnetite particles was formed. Atomic-scale transmission electron microscopy images of such a layer revealed highly ordered and parallel lattice fringes, indicating that the oxide had very high crystallinity and minimal lattice defects. In contrast, turbulent water prompted the creation of a porous oxide layer consisting of amorphous magnetite particles. Here, numerous mismatched lattice fringes were observed, indicating a prevalence of point defects within the oxide structure. These differences in oxide properties are attributed to hydrodynamic shear stress induced by turbulent flow. These findings provide atomic-level insights into how carbon steel corrosion accelerates in fast-flowing water.

Charge/discharge performance of flame-synthesized TiO2/C composite nanoparticles as anode materials

A flame-synthesized TiO2-based anode material was developed by conducting in-situ composition of TiO2 particles and amorphous carbon particles in a flame. The particle characteristics of the collected composite particles were subsequently examined, and the performances of lithium-ion secondary batteries that used these composite particles as anode materials were measured and evaluated. The aggregates of synthesized and collected particles were confirmed through SEM, EDS, and XRD analysis, revealing a mixture of amorphous carbon particles and TiO2 particles with ranging in size from about 40 to 80 nm. Analysis of the charge/discharge test results on these coin cells indicates that TiO2 and amorphous carbon determine capacity retention and discharge capacity, respectively. Considering both capacity and retention of the cells, optimal flame synthesis conditions were found.

Assessment of the physical stability of cold brew coffee in retorted beverages

In recent years, the coffee market has launched many ready-to-drink cold brew coffee beverages (CBC). When bottled, producers face issues with the stability as consumers perceive the sedimentation phenomenon as a quality defect. As the physical stability in CBC is an emerging topic, it is necessary to characterize the sediment and understand its origin to identify mitigation alternatives. In this regard, regular and decaffeinated CBC in glass bottles over a period of 60 days were analyzed by microscopy and particle size distribution. Nano, amorphous and semi-crystalline particles were identified. Nanoparticles increased in the ∼0.1 μm range in the sediment of the regular CBC. Caffeine (+10%) and chlorogenic acid (CQAs) levels (+50%) in the supernatant filtrate increased after 60 days, which by scanning electron microscopy (SEM) revealed the topology of the identified particles, with a clear presence of the crystalline needles of caffeine, protein and potassium. X-ray diffraction analysis revealed that some peaks (3 out of 10), were associated with caffeine and sucrose, suggesting a complexation from the CQA presence; and supporting that the sediment might be mostly potassium chlorogenate complex. As the phenomenon was prevalent in the regular CBC, the presence of caffeine in the formation is key.

Effect of alkali metal salt addition on disintegration of titania particles precipitated from tetraethyl orthotitanate in ethanol

AbstractInline (or in situ) photon density wave spectroscopy was used to monitor the disintegration of secondary titania particles into their primary particles. Photon density wave spectroscopy can be applied to determine the reduced scattering coefficient of a dispersion without dilution or calibration, and thus enables process analysis in materials that are usually unsuitable for established particle characterization techniques. In this work, amorphous titania particles were precipitated from tetraethyl orthotitanate in ethanol by addition of water in presence of different alkali metal salts (NaCl, KCl, CsCl, K2SO4) with concentrations between 0 and 1.6 mM. The present results suggest that the synthesized titania secondary particles disintegrate into their primary particles if the electrostatic repulsion between the primary particles is promoted. This can be achieved by an increased alkali chloride concentration in the synthesis or by addition of larger alkali metal ions. In contrast, the particles are only weakly charged upon addition of sulfate ions, and the disintegration stops. The conclusions drawn from photon density wave spectroscopy results are supported by gravimetric determination of the particle yield, dynamic light scattering measurements, zeta‐potential measurements, and electron micrographs. Additionally, the disintegration was driven to completion by addition of hydrochloric acid to create a transparent suspension of titania primary particles as small as 4.7 nm.

The Early Aptian Oceanic Anoxic event (OAE-1a) of the uppermost M'Cherga formation of northern Tunisia: Geochemical characterization and inferred petroleum potential

The Early Aptian organic-rich deep marine deposits of the upper Member of the M'Cherga Formation (Valanginian-Aptian) of northern Tunisia were studied based on a multidisciplinary approach including biostratigraphy, sedimentology and organic geochemistry. This study is based on the analysis of 128 samples collected from three sections (Oued Bazina, Djebba and Tel Ghozlene) selected from the salt dome zone (SDZ) and one section of Jebel Oust, situated westward of the Tunisian range. This work is supplemented by previous research undertaken on Oued Zarga and Jebel Ammar sections. Taxonomic analysis of previous and new data (ammonites and planktonic foraminifera) indicate that three informal lithological units rich in organic matter (U1, U2 and U3) are of Early Aptian age, covering both Blowiella blowi and Leupoldina cabri planktonic foraminiferal zones and indiscriminate Lowermost Aptian to the Deshayesites deshayesi – Dufrenoyia furcata ammonite Zones interval.The Rock-Eval analytical results indicate that the studied Early Aptian strata are relatively rich in total organic carbon (TOC) content with values reaching 4.6 % within the U3 (Leupoldina cabri biozone). The latter occurring in the different studied sections constitutes an important deepening phase related to a global sea-level rise testified by the development of well laminated platy limestones containing abundant ammonites and radiolaria. This unit (U3), covering Leupoldina cabri planktonic foraminiferal zone and Deshayesites deshayesi to Dufrenoyia furcata ammonite Zones interval records the Oceanic Anoxic Event -1a (OAE-1a).The palynofacies assemblages show that the organic matter is mainly represented by amorphous particles. The Tmax values ranging from 437 °C to 456 °C (Mean Tmax: 446 °C) and the measured vitrinite reflectance ranging from 0.79 to 1.03 %, indicate that most samples are early mature except for those of the Tel Ghozlene (TG) section which are within the peak oil-generation-window. Lateral facies and thickness variation, in addition to the organic matter distribution throughout the studied domains, strongly suggest the imprint of salt tectonics both on the sedimentological pattern and associated anoxia during the Aptian. Maturation of the organic-rich facies occurred during the Upper Cretaceous-Paleogene compressional phase and associated salt dome remobilization. Source rocks, developed in the Upper Member of the M'Cherga Formation, are attributed to the OAE1a Event and should be considered when reviewing the petroleum potential of conventional and unconventional resources in northern Tunisia.

Saharan dust induces the lung disease-related cytokines granulocyte–macrophage colony-stimulating factor and granulocyte colony-stimulating factor

Desert dust exposure is associated with adverse respiratory health effects. Desert dust is a complex pollutant mixtures that includes respirable crystalline and amorphous particles, metals, and microbial constituents. Given the health effects of desert dust and its heterogeneity, as yet unidentified harmful biological pathways may be triggered. Therefore, we exposed human in vitro air–liquid interface co-cultures of alveolar epithelial A549 cells and THP-1 macrophages to Saharan dust (SD). For comparison, we used the known pulmonary toxicant DQ12 quartz dust. Via RNA sequencing, we identified that SD but not DQ12 increased the gene expression of granulocyte–macrophage colony-stimulating factor (GMCSF) and granulocyte colony-stimulating factor (GCSF). These findings were confirmed by quantitative reverse transcriptase PCR. SD dose-dependently upregulated GMCSF and GCSF expression with significant 7 and 9-fold changes, respectively, at the highest tested concentration of 31 µg/cm2. Furthermore, we observed that SD significantly enhanced the secretion of GM-CSF and G-CSF by 2-fold. Both cytokines have previously been associated with lung diseases such as asthma and fibrosis. Hence, we present two molecular messengers that may contribute to the adverse health effects of desert dust and might serve as drug targets for this globally relevant non-anthropogenic air pollutant.

Investigation of the molecular switching process between spin crossover states of triazole complexes as basis for optical sensing applications.

With the advent of the first laser sources and suitable detectors, optical sensor applications immediately also came into focus. During the last decades, a huge variety of optical sensor concepts were developed, yet the forecast for the future application potential appears even larger. In this context, the development of new sensor probes at different scales down to the atomic or molecular level open new avenues for research and development. We investigated an iron based triazole molecular spin-crossover complex changing its absorption characteristics significantly by varying environmental parameters such as humidity, temperature, magnetic or electric field, respectively, with respect to its suitability for a new class of versatile molecular sensor probes. Hereby, besides the investigation of synthesized pure bulk material using different analyzing methods, we also studied amorphous micro particles which were applied in or onto optical waveguide structures. We found that significant changes of the reflection spectra can also be obtained after combining the particles with different types of optical waveguides.The obtained results demonstrate the suitability of the material complex for a broad field of future sensor applications.

Magnetoviscous properties of Fe-based amorphous magnetic fluids

Fe-Zr-B amorphous magnetic fluid has been prepared by a chemical reduction method. X-ray diffraction, transmission electron microscope and vibrating sample magnetometer have been utilized for the characterization of the structure, morphology, and magnetic property of Fe-based amorphous magnetic fluids. Besides, the magnetoviscous properties were also investigated. The results indicate that the Fe-Zr-B particles possess a non-crystalline structure with a particle size below 30 nm. The saturation magnetization of the amorphous particles is approximately 55 emu/g, exhibiting extremely low remanent magnetization and coercivity. We also investigated a parameter named Δη*=ηup-ηdown/ηdown, which characterizes the hysteresis effect between viscosity vs magnetic field. The results show that the relatively reduced viscosity △η* is negative below 124 mT, and becomes positive when the magnetic field is higher than 124 mT. We reveal the inverse associations between viscosity and magnetic fields, which can be attributed to the combined influence of thixotropy and magnetic fields. These discoveries present a fresh perspective on the magnetoviscous behavior of magnetic fluids.

In vitro assessment and surface morphology of copper-silver co-doped ordered mesoporous antifungal bioactive glasses

Stöber process is a desirable and less time-consuming method for preparing bioactive glass (BG) as an alternative to sol-gel and melt-quenching. The process produces monodispersed BG structures with amorphous particles that can be modified with other precursors to get the desired properties. Substituting alkaline metals within BG structures provides favorable physicochemical and bioactivity properties. The current study synthesized a new glass family co-doped with silver and copper and investigated the surface morphology, textural properties, and therapeutic functions. The presence of silver and copper ions in the glass network was confirmed via Scanning Electron Microscopy (SEM) images, demonstrating nano spheroid particles with a particle size of 95 ± 15 nm. The Brunauer–Emmett–Teller (BET) and Barrett–Joyner–Halenda (BJH) analysis revealed mesoporous particles with pore diameters between 3 ± 0.8 nm, closely related to their surface area. Furthermore, the acellular assay showed apatite layer formation and distinct X-ray Diffraction analysis (XRD) peaks were detected upon immersion of particles in simulated body fluid for 7 days. In addition, doping bioactive glass has demonstrated antifungal activity with Ag2O and CuO, which appears as a promising approach, indicating that incorporating silver and copper ions inhibited the growth of candida albicans, thus suggesting that this type of bioactive glass could exhibit potential applications in bone and tissue engineering, drug delivery, and antifungal as well as for bioactive coatings.

Tubular Nanoclay-Enhanced Calcium Phosphate Mineralization and Assembly to Impart High Stiffness and Antimicrobial Properties.

Achieving superior mechanical properties of composite materials in artificially engineered materials is a great challenge due to technical bottlenecks in the size and morphological modulation of inorganic nanominerals. Hence, a "bioprocess-inspired fabrication" is proposed to create multilayered organic-inorganic columnar structures. The sequential assembly of halloysite nanotubes (HNTs), polyelectrolytes (PAAs), and calcium phosphates (CaPs) results in organic-inorganic structures. PAA plays a crucial role in controlling the formation of CaP, guiding it into amorphous particles with smaller nanosizes. The introduction of HNT induces the assembly and maturation of CaP-PAA, leading to the formation of a highly crystalline hydroxyapatite. Poly(vinyl alcohol) was then woven into HNT-encapsulated hydroxyapatite nanorods, resulting in composite materials with basic hierarchical structures across multiple scales. The fabricated composite exhibits exceptional hardness (4.27 ± 0.33 GPa) and flexural strength (101.25 ± 1.72 MPa), surpassing those of most previously developed biological hard tissue materials. Additionally, the composite demonstrates effective antibacterial properties and corrosion resistance, attributed to the dense crystalline phase of CaP. This innovative approach showcases the potential of clay minerals, particularly HNT, in the advancement of biomaterial design. The outstanding mechanical and antimicrobial properties of clay-based composites make them a promising candidate for applications in hard tissue repair, offering versatility in biomedicine and engineering.

Amorphous diamond embedded in dense boron nitride with excellent mechanical properties

Diamond and cubic boron nitride (BN) are important materials with a variety of technological and industrial applications; however, overcoming the intrinsic brittleness of these materials is still a challenge. Here, we synthesize a compound of crystalline BN and amorphous diamond-like carbon through BN nanotubes and fullerene under high pressure and high temperature conditions. The obtained composite exhibits excellent combination of a measured Vickers’ hardness of 86.2 GPa and fracture toughness of 10.2 MPa m1/2. Morphological and structural characterizations reveal that the amorphous diamond-like carbon is homogeneously embedded in a matrix of dense BN. The formation of the amorphous diamond-like carbon particles within the polycrystalline BN can effectively impede the migration of crack tips when the compound is subjected to the plastic deformation, in which most of crack tips are forced to deflect or confined near the boundaries of dense BN and amorphous diamond particles. The crystalline-amorphous composite strengthening presented here may provide a promising strategy for the further improvement of mechanical properties of hard or superhard materials.

Peptide Amphiphile‐Mediated Assembly and Fusion of Anisotropic Amorphous Particles for Enamel Remineralization

AbstractEnamel remineralization, which attempts to generate a mineral layer structurally similar to native enamel and restore its mechanical properties, remains a significant challenge. Here, rationally designed peptide amphiphile (PA) molecules bind to amorphous calcium phosphate (ACP) particles via electrostatic interactions, imparting anisotropic properties that drive PA‐modified ACP to form spindle‐shaped aggregates. Furthermore, some residual PA molecules may further regulate crystallization and facilitate the formation of well‐aligned hydroxyapatite bundles. Additionally, the involvement of PA can mediate the ordered deposition and fusion of ACP on the enamel surface, and construct the crystalline‐amorphous mineralization front with a continuous structure. This mineralization front ensures epitaxially oriented growth of enamel crystals and achieves a structurally ordered mineral layer similar to that of native enamel, while the mechanical performance is effectively restored. More significantly, the thickness of the newly formed mineral layer can be augmented through cyclic remineralization, benefitting the design of products intended for practical enamel repair.

Risedronate-functionalized manganese-hydroxyapatite amorphous particles: A potent adjuvant for subunit vaccines and cancer immunotherapy

The cGAS-STING pathway and the Mevalonate Pathway are druggable targets for vaccine adjuvant discovery. Manganese (Mn) and bisphosphonates are known to exert adjuvant effects by targeting these two pathways, respectively. This study found the synergistic potential of the two pathways in enhancing immune response. Risedronate (Ris) significantly amplified the Mn adjuvant early antibody response by 166-fold and fortified its cellular immunity. However, direct combination of Mn2+ and Ris resulted in increased adjuvant toxicity (40% mouse mortality). By the combination of doping property of hydroxyapatite (HA) and its high affinity for Ris, we designed Ris-functionalized Mn-HA micro-nanoparticles as an organic-inorganic hybrid adjuvant, named MnHARis. MnHARis alleviated adjuvant toxicity (100% vs. 60% survival rate) and exhibited good long-term stability. When formulated with the varicella-zoster virus glycoprotein E (gE) antigen, MnHARis triggered a 274.3-fold increase in IgG titers and a 61.3-fold surge in neutralization titers while maintaining a better long-term humoral immunity compared to the aluminum adjuvant. Its efficacy spanned other antigens, including ovalbumin, HPV18 VLP, and SARS-CoV-2 spike protein. Notably, the cellular immunity elicited by the group of gE + MnHARis was comparable to the renowned Shingrix®. Moreover, intratumoral co-administration with an anti-trophoblast cell surface antigen 2 nanobody revealed synergistic antitumor capabilities. These findings underscore the potential of MnHARis as a potent adjuvant for augmenting vaccine immune responses and improving cancer immunotherapy outcomes.

Redistribution of dopants between amorphous and crystalline phases in ZrO2–SiO2 nanoceramics

AbstractExtensive efforts have been devoted to investigate the distribution of dopants in ceramics. However, one critical question remained barely explored, which is the redistribution of dopants between amorphous and crystalline phases during fast sintering of ceramics. Here we address this gap by observing the redistribution of five selected dopants (Y, Ce, Yb, Hf, and Ta) in ZrO2–SiO2 nanoceramics during sintering. We designed two groups of experiments: In group one, dual‐phase amorphous particles were sintered with multicomponent crystalline ones. The former particles were ZrO2–SiO2 glass, whereas the latter ones consisted of ZrO2 solid‐solution nanocrystallites (SSNCs) embedded in an oxide glass containing Zr, Si, Y, Ce, Hf, Yb, and Ta. In group two, dual‐phase crystalline particles were sintered with multicomponent amorphous ones. The former particles were composed of ZrO2 nanocrystallites (NCs) embedded in an amorphous SiO2 matrix, whereas the latter ones were oxide glass containing Zr, Si, Y, Ce, Hf, Yb, and Ta. Redistribution of the dopants from the glass to ZrO2 NCs occurred in the two groups, that is, the five dopants migrated from the glass matrix into the ZrO2 NCs, forming ZrO2 SSNCs. The redistribution of the dopants not only increased the configuration entropy of the ZrO2 NCs but also benefited the network structure integrity of SiO2 glass. The dopant redistribution process was driven by the minimization of the studied material's free energy. The reported results are important for understanding the redistribution behaviors of dopants and are expected to provide new insights to design new ceramics via the multielement co‐doping strategy.