Shell Formation Research Articles

Possible roles of Wnt in the shell growth of the pond snail Lymnaea stagnalis

Although the mechanisms of molluscan shell growth have been studied using mathematical models, little is known about the molecular basis underpinning shell morphogenesis. Here, we performed Wnt activation experiments to elucidate the potential roles of Wnt signaling in the shell growth of Lymnaea stagnalis. In general, we observed following three types of shell malformations in both dose- and developmental stage-dependent manners: (i) cap-shaped shell, (ii) cap-shaped shell with hydropic soft tissues, and (iii) compressed shell with a smaller number of coiling. We analyzed the morphologies of these malformed shells using the growing tube model, revealing that the compressed malformations show significantly larger values for T (torsion), with no significant changes in the values for the remaining parameters E (expansion) and C (curvature). We also found that cap-shaped malformations have significantly larger values for E, suggesting that the effects of BIO on shell formation may change during growth. Since the changes in T and/or E parameter values can greatly alter the shell morphologies from a planispiral or a cap-shaped one to various three-dimensional helices, changes in shell developmental processes possibly controlled by Wnt signaling may account for at least a part of the evolution of diverse shell forms in molluscs.

Phase changes in burning precursor-laden single droplets leading to puffing and micro-explosion

When producing metal-oxide nanoparticles via flame spray pyrolysis, precursor-laden droplets are ignited and undergo thermally induced disintegration, called ‘puffing’ and ‘micro-explosion’. In a manner that is not fully understood, these processes are associated with the formation of dispersed phases inside the droplets. This work aims at visualizing the interior of precursor-laden burning single droplets via diffuse back illumination and microscopic high-speed imaging. Solutions containing iron(III) nitrate nonahydrate (INN) and tin(II) 2-ethylhexanoate (Sn-EH) were dispersed into single droplets of sub-100 μm diameter that were ignited by passing through a heated coil. At low precursor concentration, 50% of the INN-laden droplets indicate a gas bubble of about 5 μm diameter in the center of the droplet. The bubble persists for several hundred microseconds at a similar size. In almost all of these cases, the bubble expands at some point and the droplet ends up in a micro-explosion. In some of these instances, the droplet’s surface shows spatial brightness modulations, i.e., surface undulations, indicating the formation of a viscous shell. With increasing INN concentration, the fraction of droplets showing surface undulations, gas bubbles, and micro-explosions drastically decreases. This may be associated with a more rigid viscous shell and reduced mobility of bubbles. Bright incandescent streaks originating from the disrupting INN-laden droplets, may indicate sub-micrometer droplets or particles from within the droplets or formed in the gas phase. In contrast, Sn-EH-laden droplets show very fast disruptions, typically less than 10 μs from first visible deformation to ejection of secondary droplets. Bubbles and surface undulations were not observed.Graphical abstract

The impact of non-isothermal adsorption of dissolved gas on drying of acoustically levitated slurry droplet

In this study, we developed a transient convective heat and mass transfer model of an acoustically levitated slurry droplet evaporating in an atmosphere of air, water vapor, and soluble gas. The advanced model considers the effects of acoustic streaming, forced convection, non-isothermal gas absorption, and adsorption of dissolved gas on the evaporation rate of a liquid droplet containing small active solid particles. Adsorption of dissolved in a droplet soluble gas by solid particles leads to decreased dissolved gas concentration in a liquid droplet. A reduction in dissolved gas concentration in a liquid droplet causes an increase in the mass flux of active soluble gas from a gaseous phase to a slurry droplet, which causes a rise in the heating effect of absorption and an increase in evaporation rate of a droplet. The heat effect of adsorption also intensifies the evaporation rate. It is shown that the time of porous shell formation is essentially shorter when solid particles in slurry droplets are active compared to inert particles.

Microfluidics-based stable production of monodisperse giant unilamellar vesicles by oil-phase removal from double emulsion

Giant liposomes, or giant unilamellar vesicles (GUVs), have been utilized as cell-size bioreactors to replicate the physical and chemical properties of biological cells. However, conventional methods for preparing GUVs typically lack precise control over their size. Several research groups have recently developed microfluidic techniques to create monodisperse GUVs by generating water-in-oil-in-water (W/O/W) droplets with a thin oil layer that subsequently transform into GUVs. However, the formation of a thin oil shell requires the intricate control of the flow rate, which can be both challenging and unstable. In this study, we investigated the design of a two-step flow-focusing microfluidic channel to produce stable W/O/W droplets. These droplets underwent substantial oil layer reduction through spontaneous removal by fluidic shear forces. Consequently, the majority of the oil layer in the W/O/W droplets was reduced, improving uniformity of GUVs.

Fabrication of hydrogel mini-capsules as carrier systems

Conventional drug administration often results in systemic action, thus needing high dosages and leading to potentially pronounced side effects. Targeted delivery, employing carriers like nanoparticles, aims to release drugs at a target site, but only a small fraction of nanoparticles actually reaches it. Microrobots have been proposed to overcome this issue since they can be guided to hard-to-reach sites and locally deliver payloads. To enhance their functionality, we propose microrobots made as deformable capsules with hydrogel shells and aqueous cores, having the potential added advantages of biocompatibility, permeability, and stimulus-responsiveness. Endowing microrobots with deformability could allow them to navigate inside capillaries and cross barriers to finally reach the target site. In this study, we present a cost-effective method for fabricating core-shell structures without the use of organic solvents, surfactants, or extreme pH conditions unlike other techniques (e.g. Layer by Layer). The process begins with the dripping of a mixture of hydrogels, agarose and alginate, into a solution to gelate the drops into beads. After they are loaded with calcium ions at different concentrations, they are immersed in an alginate solution to form the shell. Finally, the beads are heated to let the agarose melt and diffuse out, leaving a liquid core. By varying the concentration of calcium ions, we obtain shells of different thicknesses. To estimate it, we have developed a method using the colour intensity from microscope images. This allowed us to observe that lowering the calcium ions concentration below a threshold does not lead to the formation of continuous shells. For higher concentrations, although the core may remain partially gelled, continuous shells successfully form. Therefore, our fabrication process could find applications in drug delivery, encapsulation systems, and microrobotics.

Facile Synthesis of Rhodium-Based Nanocrystals in a Metastable Phase and Evaluation of Their Thermal and Catalytic Properties.

Controlling the polymorphism of metal nanocrystals is a promising strategy for enhancing properties and discovering new phenomena. However, previous studies on Rh nanocrystals have focused on their thermodynamically stable face-centered-cubic (fcc) phase. Herein, a facile synthesis of Rh-based nanocrystals featuring the metastable hexagonal close-packed (hcp) phase is reported by using Ru seeds in their native hcp phase to template the deposition of Rh atoms. The success of such phase-controlled synthesis relies on the templating effect promoted by the small lattice mismatch between Ru and Rh and the slow dropwise titration of the precursor at an elevated temperature, ensuring the layer-by-layer growth mode and thus the formation of a conformal hcp-Rh shell. Faster injection rate of Rh(III) precursor leads to the formation of a rough Rh shell in the conventional fcc phase due to accelerated reaction kinetics. Considering both thermodynamic and kinetic aspects of this system, the hcp-Rh phase is favored when the low surface energy from smooth overlayers balances the high bulk energy of the metastable phase, achieved through tight control of reaction rates and deposition patterns. These Ruhcp@Rhhcp core-shell nanocrystals demonstrate thermal stability up to 400°C, while exhibiting higher catalytic activity toward ethanol oxidation reaction compared to Ruhcp@Rhfcc counterparts.

Nuclear p62 condensates stabilize the promyelocytic leukemia nuclear bodies by sequestering their ubiquitin ligase RNF4

Liquid-liquid phase separation has emerged as a crucial mechanism driving the formation of membraneless biomolecular condensates, which play important roles in numerous cellular processes. These condensates, found both in the nucleus and cytoplasm, are formed through multivalent, low-affinity interactions between various molecules. P62-containing condensates serve, among other functions, as proteolytic hubs for the ubiquitin-proteasome system. In this study, we investigated the dynamic interplay between nuclear p62 condensates and promyelocytic nuclear bodies (PML-NBs). We show that p62 condensates stabilize PML-NBs under both basal conditions and following exposure to arsenic trioxide which stimulates their degradation. We further show that this effect on the stability of PML-NBs is due to sequestration of their ubiquitin E3 ligase RNF4 in the p62 condensates with subsequent rapid degradation of the ligase. The sequestration of the ligase is made possible by association between the proline-rich domain of the PML protein and the PB1 domain of p62, which results in the formation of a PML-NB shell around the p62 condensates. Importantly, these hybrid structures do not undergo fusion and mixing of their contents which leaves unsolved the mechanism of sequestration of RNF4 in the condensates. These findings suggest an additional possible mechanism of PML-NB as a tumor suppressor which is mediated via interactions between different biomolecular condensates.

Enhancing Stability of Surface Au under Oxidizing Conditions through Reduced Bulk Au Content.

Contrary to the common assumption that a higher bulk content of precious metals facilitates the preservation of more surface noble metal by serving as a reservoir for surface enrichment, we demonstrate that a lower bulk content of Au results in a more stable arrangement of Au atoms at the surface of Cu-Au nanoparticles when exposed to an O2 atmosphere. Using ambient pressure X-ray photoelectron spectroscopy, we investigate the surface segregation and oxidation behavior of Cu-Au nanoparticles across various compositions. Our results reveal that in Au-rich nanoparticles exposed to an H2 atmosphere, surface segregation prompts the formation of a continuous Au-enriched shell, which subsequently oxidizes into a complete CuOx shell upon transitioning to an O2 atmosphere. Conversely, in Au-poor nanoparticles during H2 treatment, segregation results in the emergence of Au clusters embedded within the surface layer, persisting upon exposure to O2. This unexpected phenomenon shows that reducing the bulk content of precious metals can enhance the surface stability of noble atoms under oxidizing conditions, as further demonstrated by comparing the catalytic performance of Cu-Au nanoparticles with varying Au bulk contents in CO oxidation.

Genome-wide identification and expression profiling of the Wnt gene family in three abalone species.

The Wnt gene family plays pivotal roles in a variety of biological processes including cell proliferation and differentiation, apoptosis, and embryonic development. Identifying the Wnt signaling pathway in abalone could provide a basis for elucidating growth and development mechanisms and improving quality. To identify the number, protein physicochemical properties, gene structure, phylogenetic analysis, and expression profiles of the Wnt gene family in abalone. A comprehensive genome-wide analysis was performed to identify the Wnt gene family in the genomes of three abalone species (Haliotis discus hannai, H. rubra, and H. rufescens). Ten single-copy Wnt genes were identified in each abalone species, suggesting that the number of Wnt genes was relatively conserved in Haliotis. Eight Wnt gene subfamilies, including Wnt1, Wnt4, Wnt5, Wnt6, Wnt7, Wnt10, Wnt16, and WntA, are present in all three species. Each abalone species contains two species-specific subfamilies (Wnt9 and Wnt11 in H. discus hannai, Wnt2 and Wnt11 in H. rubra, and Wnt2 and Wnt9 in H. rufescens), reflecting polymorphisms of the Wnt genes in Haliotis. Interestingly, gastropods are characterised by the loss of Wnt8, suggesting a potential evolutionary specificity in gastropods. As expected, Wnt3 is absent in all protostomes, including the abalone. In addition, spatio-temporal expression profiling revealed differential expression levels of the Wnt genes at different developmental stages and in different tissues of H. discus hannai. HdWnt5 and HdWntA might participate in several processes during larval development stages, including germ layer formation and body axis elongation. HdWnt5 may be involved in eye and tentacle development. HdWnt10 may be related to muscle development, and HdWnt6 may be involved in shell formation in abalone. To our knowledge, the results of this study, which is the first genome-wide investigation of the Wnt gene family in abalone, lay the groundwork for future research on the evolution and function of the Wnt gene family in Gastropoda.

Development of Cost-Effective Sn-Free Al-Bi-Fe Alloys for Efficient Onboard Hydrogen Production through Al–Water Reaction

Leveraging the liquid-phase immiscibility effect and phase diagram calculations, a sequence of alloy powders with varying Fe content was designed and fabricated utilizing the gas atomization method. Microstructural characterizations, employing SEM, EDS, and XRD analyses, revealed the successful formation of an incomplete shell on the surfaces of Al-Bi-Fe powders, obviating the need for Sn doping. This study systematically investigated the microstructure, hydrolysis performance, and hydrolysis process of these alloys in deionized water. Notably, Al-10Bi-7Fe exhibited the highest hydrogen production, reaching 961.0 NmL/g, while Al-10Bi-10Fe demonstrated the peak conversion rate at 92.99%. The hydrolysis activation energy of each Al-Bi-Fe alloy powder was calculated using the Arrhenius equation, indicating that a reduction in activation energy was achieved through Fe doping.

Dramatic droplet deformation through interfacial particles jamming

Droplets of one fluid in a second, immiscible fluid are typically spherical in shape due to the interfacial tension between the two fluids. Shear forces can lead to droplet deformation when they are subjected to flow, and these effects can be further modified when the droplet is stabilized by a surfactant due to a flow-induced gradients in the surfactant concentration. An alternative method of stabilizing droplets is through the use of colloidal particles, whose stabilization behavior is intrinsically different from molecular surfactants. Under the same flow condition, a gradient of particle concentration can result in the jamming of particles in regions with a high packing density, making the interface solid-like, albeit only under compression and not tension. However, how this asymmetry in the surfactant properties alters the droplet shape under shear is unknown. Here, we show that shear of particle-stabilized droplets can lead to a remarkable array of shape deformations as the droplets flow through a constrained microchannel. The shear-induced migration of particles on the surface results in the formation of an elastic shell at the back of the droplet, which can wrinkle and invaginate, ultimately leading to a unique core-shell structure. The shapes depend on the Peclet number of the flow, reflecting the balance of shear forces that drive the particles and diffusion that randomizes them. These findings highlight the consequences of the asymmetry in the forces between the particles and provide a unique method to controllably create droplets with a vast array of different shapes.

Effect of shell composition on watertightness and mechanical performance of cement-based capsules used as self-healing additives of cement

The aim of this work is the development of cementitious macro-capsules for self-healing cement and concrete materials. Emphasis is placed on shell properties, including size, thickness, strength, and volume to active component ratio. This enhancement is aimed at protecting the healing agent and ensuring adequate reactivity upon crack formation, surpassing survivability considerations. To this direction, core/shell particles have been produced following the pan-coating method, while different types and concentrations of setting acceleration solutions for the shell stabilization were studied. The formation of core-shell capsules encompasses the formation a spherical core through agglomeration, followed by simultaneous spraying of cement powder and a setting acceleration solution for the shell formation, under continuous rotation. The microstructural characteristics of the shell were studied through scanning electron microscopy (SEM), while the reactivity of the protected core (reactive agent) inside the hardened mortar mixtures was evaluated using thermogravimetric analysis (TGA). Moreover, the crushing load of the capsules under compression and their survivability during mixing process were examined and interpreted in relation to their diameter, circularity, and shell thickness.The results revealed the ability of the encapsulation methodology proposed to tailor the shell properties and modify the capsule properties so as satisfy the requirements of different applications. The use of setting accelerators during shell formation proved essential for enhancing the density and the strength of the shell layer. As a consequence, this leads to macro-scale capsules with elevated survivability rate and core reactivity.

Evaporation of stable microemulsion droplets

Emulsion fuels have the potential to reduce both particulate matter and NOx emissions and can potentially improve the efficiency of combustion engines. However, their limited stability remains a critical barrier to practical use as an alternative fuel. In this study, we explore the evaporation behavior of thermodynamically stable water-in-oil microemulsions. The water-in-oil microemulsion droplets prepared from different types of oil were acoustically levitated and heated using a continuous laser at different irradiation intensities. We show that the evaporation characteristics of these microemulsions can be controlled by varying water-to-surfactant molar ratio (ω) and volume fraction of the dispersed phase (ϕ). The emulsion droplets undergo three distinct stages of evaporation, namely preheating, steady evaporation, and unsteady evaporation. During the steady evaporation phase, increasing ϕ reduces the evaporation rate for a fixed ω. It is observed that the evaporation of microemulsion is governed by the complex interplay between its constituents and their properties. We propose a parameter (η) denoting the volume fraction ratio between volatile and nonvolatile components, which indicates the cumulative influence of various factors affecting the evaporation process. The evaporation of microemulsions eventually leads to the formation of solid spherical shells, which may undergo buckling. The distinction in the morphology of these shells is explored in detail using scanning electron microscopy imaging.

Additive manufacturing of sustainable and heat-resistant Al-Fe-Mo-Si-Zr alloys

Improving the sustainability of metals and alloys is essential for slowing down global warming. The reason is that their extraction and production stand for about 40% of all greenhouse gas emissions in the industrial sector. This motivates new alloy design and processing criteria such as the (1) preferred use of abundant and sustainable alloying elements and (2) improved material tolerance against impurity intrusion from recycling. In this context, additive manufacturing (AM) is attractive, through rapid solidification, capable of quenching impurities into a solid solution state, avoiding formation of large intermetallics and introduction of metastable phases. Here, by using this approach we show how iron, an important scrap-related contaminant in aluminum alloys, can be turned from a harmful into a valuable ingredient. Specifically, the addition of Mo and Si facilitates the formation of beneficial metastable body-centred cubic (BCC) Al12(Fe, Mo)3Si phase, instead of more stable but detrimental intermetallic variants commonly observed in Al-Fe alloys. The as-built microstructures have excellent thermal stability, tested up to 200hours at 300 °C, because of low diffusivity of Fe and the formation of Zr shell. We find that for such supersaturated alloys, two issues are important, namely (a) the heterogeneous microstructures in the as-built condition, (b) the evolution of metastable precipitates during heating. We suggest that this type of approach help to guide sustainable alloy design via AM and other rapid solidification processes.

Nonthermal Signatures of Radiative Supernova Remnants

The end of supernova remnant (SNR) evolution is characterized by a so-called “radiative” stage, in which efficient cooling of the hot bubble inside the forward shock slows expansion, leading to eventual shock breakup. Understanding SNR evolution at this stage is vital for predicting feedback in galaxies, since SNRs are expected to deposit their energy and momentum into the interstellar medium at the ends of their lives. A key prediction of SNR evolutionary models is the formation at the onset of the radiative stage of a cold, dense shell behind the forward shock. However, searches for these shells via their neutral hydrogen emission have had limited success. We instead introduce an independent observational signal of shell formation arising from the interaction between nonthermal particles accelerated by the SNR forward shock (cosmic rays) and the dense shell. Using a semi-analytic model of particle acceleration based on state-of-the-art simulations coupled with a high-resolution hydrodynamic model of SNR evolution, we predict the nonthermal emission that arises from this interaction. We demonstrate that the onset of the radiative stage leads to nonthermal signatures from radio to gamma rays, including radio and gamma-ray brightening by nearly 2 orders of magnitude. Such a signature may be detectable with current instruments, and will be resolvable with the next generation of gamma-ray telescopes (namely, the Cherenkov Telescope Array).

Biomineralization and biomechanical trade-offs under heterogeneous environments in the eastern oyster Crassostrea virginica

ABSTRACT Accurate biological models are critical to reliably predict vulnerability of marine organisms and ecosystems to rapid environmental changes. Current predictions on the biological impacts of climate change and human-caused disturbances primarily stem from controlled experiments but lack assessments of the mechanisms underlying biotic variations in natural systems, especially for habitat-forming, climate-sensitive species with key ecological roles. This study aimed to characterize and quantify spatial patterns of shell biomineralization and biomechanical properties in a key reef-building oyster, Crassostrea virginica, collected from restored reefs along natural estuarine gradients in the Hudson River Estuary (NY, USA). We characterized patterns of oyster shell deposition, structure, composition and mechanical performance at the macro- and microscale. Eastern oysters show a strong capacity for adjustments in shell biomineralization and biomechanics to maintain shell production and protective functions. We reveal salinity as a key predictor of oyster shell structure, mechanical integrity and resistance to dissolution, and describe the functional role of chalky calcite in shaping shell mechanical performance. Changes in shell production along salinity gradients indicate formation of shells with (1) high mechanical resistance but increased vulnerability to dissolution under marine conditions and (2) lower structural integrity but higher protection from dissolution under brackish conditions. Our work illustrates that biomineralization and biomechanical trade-offs may act as mechanisms in eastern oysters to maintain overall performance under heterogeneous estuarine environments and could represent a cornerstone for calcifying organisms to acclimate and maintain their ecological functions in a rapidly changing climate.

Molecular modeling and simulation of organic electrolyte solutions for lithium ion batteries.

Multi-criteria optimization is used for developing molecular models for ethylene carbonate (EC) and propylene carbonate (PC), organic solvents commonly used in Li-ion batteries. The molecular geometry and partial charges of the solvents are obtained from quantum mechanical calculations. Using a novel optimization strategy that combines systematic variations of the Lennard-Jones parameters with a reduced units approach, the models are fitted to experimental data on the liquid density, vapor pressure, relative permittivity, and self-diffusion coefficient. Since no experimental data for the self-diffusion coefficient of pure EC were available in the literature, they are measured in this work using a gradient-based nuclear magnetic resonance technique. For all pure component properties, excellent agreement between experiment and simulation is obtained. Moreover, the predictive capabilities of the new solvent models are assessed by comparison to experimental data for the liquid density and relative permittivity of mixtures of EC and PC. In addition, molecular models for the anions PF6-, BF4-, and ClO4- in solutions of their lithium electrolytes in PC are developed using experimental data on the solution densities. Finally, the self-diffusion coefficients of LiPF6 in PC and in aqueous solution are predicted and compared, showing that diffusion is much slower in the organic solution due to the formation of larger solvent shells around the ions. Furthermore, an analysis of the radial distribution functions in these solutions suggests that the ions have much less impact on the structure of the solvent PC than on water.

Microfluidic-assisted synthesis of hybrid calcium carbonate/silver microparticles

The development of advanced methods for the synthesis of nano- and microparticles for biomedical applications is of considerable interest. A method for the synthesis of submicron silver-shelled calcium carbonate particles using a microfluidic chip designed to provide control over particle formation is proposed. Precise control of reaction parameters enables the formation of silver shell and calcium carbonate particles in a controlled manner. The distribution of pores in the hybrid particles was analyzed using small-angle X-ray scattering, which provided insight into the complex structure of the pores. The results provide information on particle morphology and may facilitate the development of new calcium carbonate-based materials for various applications.

Concurrent processes in the time-resolved solvation and Coulomb ejection of sodium ions in helium nanodroplets

Recent pump-probe experiments [Albrechtsen et al., Nature 623, 319 (2023)] have explored the gradual solvation of sodium cations in contact with helium nanodroplets, using a fully solvated xenon atom as a probe exerting a repulsive interaction after its own ionization. In this communication, we computationally examine by means of atomistic ring-polymer molecular dynamics the mechanisms of successive ionizations, shell formation, and Coulomb ejection that all take place within tens of picoseconds and show that their interplay subtly depends on the time delay between the two ionizations but also on the droplet size. The possibility of forming solvated Na+Xe non-covalent complexes under a few tens of picoseconds in such experiments is ruled out based on fragment distributions.

Unravelling molecular origins of improved tribological properties of amino acid ionic liquid water-based lubricants

In the quest for sustainable lubrication, this study explores the potential of water-based lubricants (WBLs) with amino acid ionic liquid (AAIL) additives. The research combines experimental and reactive molecular dynamics (MD) simulations to assess the tribological and rheological enhancements provided by AAILs. Specifically, tetrabutylphosphonium (P4444) cations paired with Serine (Ser) and Tryptophan (Trp) anions were mixed into water to create AAIL WBLs. The introduction of AAILs significantly improved the lubricants’ rheological properties and reduced the coefficient of friction by up to 34 %. This reduction is attributed to the formation of hydration shells around the amino acid anions, which create a chemically adsorbed tribofilm on iron oxide surfaces, and P4444 cations that establish a load-bearing layer in the middle regions of the lubricant. This dual-layer structure, supported by hydration lubrication, effectively maintains lubricant fluidity while bearing substantial loads. Among the AAIL WBLs tested, those with a thicker, more stable, hydrated amino acid tribofilm demonstrated more significant friction reduction. These insights into the molecular mechanisms behind AAIL WBLs’ tribological behaviour underscore their promise as eco-friendly lubricants, contributing to advancing a circular economy in industries reliant on lubrication.