Spontaneous Liquefaction of Solid Metal-Liquid Metal Interfaces in Colloidal Binary Alloys.

Crystallization of alloys from a molten state is a fundamental process underpinning metallurgy. Here the direct imaging of an intermetallic precipitation reaction at equilibrium in a liquid-metal environment is demonstrated. It is shown that the outer layers of a solidified intermetallic are surprisingly unstable to the depths of several nanometers, fluctuating between a crystalline and a liquid state. This effect, referred to herein as crystal interface liquefaction, is observed at remarkably low temperatures and results in highly unstable crystal interfaces at temperatures exceeding 200 K below the bulk melting point of the solid. In general, any liquefaction process would occur at or close to the formal melting point of a solid, thus differentiating the observed liquefaction phenomenon from other processes such as surface pre-melting or conventional bulk melting. Crystal interface liquefaction is observed in a variety of binary alloy systems and as such, the findings may impact the understanding of crystallization and solidification processes in metallic systems and alloys more generally.

Mechanism behind the Controlled Generation of Liquid Metal Nanoparticles by Mechanical Agitation.

The size-controlled synthesis of liquid metal nanoparticles is necessary in a variety of applications. Sonication is a common method for breaking down bulk liquid metals into small particles, yet the influence of critical factors such as liquid metal composition has remained elusive. Our study employs high-speed imaging to unravel the mechanism of liquid metal particle formation during mechanical agitation. Gallium-based liquid metals, with and without secondary metals of bismuth, indium, and tin, are analyzed to observe the effect of cavitation and surface eruption during sonication and particle release. The impact of the secondary metal inclusion is investigated on liquid metals' surface tension, solution turbidity, and size distribution of the generated particles. Our work evidences that there is an inverse relationship between the surface tension and the ability of liquid metals to be broken down by sonication. We show that even for 0.22 at. % of bismuth in gallium, the surface tension is significantly decreased from 558 to 417 mN/m (measured in Milli-Q water), resulting in an enhanced particle generation rate: 3.6 times increase in turbidity and ∼43% reduction in the size of particles for bismuth in gallium liquid alloy compared to liquid gallium for the same sonication duration. The effect of particles' size on the photocatalysis of the annealed particles is also presented to show the applicability of the process in a proof-of-concept demonstration. This work contributes to a broader understanding of the synthesis of nanoparticles, with controlled size and characteristics, via mechanical agitation of liquid metals for diverse applications.

Coffee brewing sonoreactor for reducing the time of cold brew from several hours to minutes while maintaining sensory attributes.

This research designed and developed an ultrasonic reactor for a fast and on demand production of cold brew coffee, remarkably reducing the brewing time from 24 h to less than 3 min. The technology was engineered by utilizing resonance to induce ultrasonic waves around the walls of the brewing basket of an espresso machine. The sound transmission system comprised a transducer, a horn and a brewing basket. This arrangement transformed the coffee basket into an effective sonoreactor that injected sound waves at multiple points through its walls, thereby generating multiple regions for acoustic cavitation within the reactor. Furthermore, acoustic streaming induced greater mixing and enhanced mass transfer during brewing. The design was accomplished by modeling the transmission of sound, and acoustic cavitation. Brew characterization and chemical composition analysis was performed, considering factors such as pH, acidity, color, and the composition of caffeine, fatty acids, and volatiles. The efficiency of the extraction increased by decreasing the basket loading percentage (BLP). For instance, sonicating at 100 W doubled the extraction yield and caffeine concentration, from 15.05 % to 33.44 % at BLP = 33 %, and from 0.91 mg/mL to 1.84 mg/mL at BLP = 67 %, respectively. The total fatty acids increased from 1.16 mg/mL to 9.20 mg/mL, representing an eightfold increase, at BLP = 33 %. Finally, a sensory analysis was conducted to evaluate appearance, aroma, texture, flavor, and aftertaste, which demonstrated that coffee brewed for 1 and 3 min in the sonoreactor exhibited almost undistinguishable properties compared to a standard 24 h brewing without ultrasound.

Review article: Current status and future directions of ingestible electronic devices in gastroenterology.

BACKGROUND: Advances in microelectronics have greatly expanded the capabilities and clinical potential of ingestible electronic devices. AIM: To provide an overview of the structure and potential impact of ingestible devices in development that are relevant to the gastrointestinal tract. METHODS: We performed a detailed literature search to inform this narrative review. RESULTS: Technical success of ingestible electronic devices relies on the ability to miniaturise the microelectronic circuits, sensors and components for interventional functions while being sufficiently powered to fulfil the intended function. These devices offer the advantages of being convenient and minimally invasive, with real-time assessment often possible and with minimal interference to normal physiology. Safety has not been a limitation, but defining and controlling device location in the gastrointestinal tract remains challenging. The success of capsule endoscopy has buoyed enthusiasm for the concepts, but few ingestible devices have reached clinical practice to date, partly due to the novelty of the information they provide and also due to the challenges of adding this novel technology to established clinical paradigms. Nonetheless, with ongoing technological advancement and as understanding of their potential impact emerges, acceptance of such technology will grow. These devices have the capacity to provide unique insight into gastrointestinal physiology and pathophysiology. Interventional functions, such as sampling of tissue or luminal contents and delivery of therapies, may further enhance their ability to sharpen gastroenterological diagnoses, monitoring and treatment. CONCLUSIONS: The development of miniaturised ingestible microelectronic-based devices offers exciting prospects for enhancing gastroenterological research and the delivery of personalised, point-of-care medicine.

Liquid Metal Doping Induced Asymmetry in Two-Dimensional Metal Oxides.

The emergence of ferroelectricity in two-dimensional (2D) metal oxides is a topic of significant technological interest; however, many 2D metal oxides lack intrinsic ferroelectric properties. Therefore, introducing asymmetry provides access to a broader range of 2D materials within the ferroelectric family. Here, the generation of asymmetry in 2D SnO by doping the material with Hf0.5 Zr0.5 O2 (HZO) is demonstrated. A liquid metal process as a doping strategy for the preparation of 2D HZO-doped SnO with robust ferroelectric characteristics is implemented. This technology takes advantage of the selective interface enrichment of molten Sn with HZO crystallites. Molecular dynamics simulations indicate a strong tendency of Hf and Zr atoms to migrate toward the surface of liquid metal and embed themselves within the growing oxide layer in the form of HZO. Thus, the liquid metal-based harvesting/doping technique is a feasible approach devised for producing novel 2D metal oxides with induced ferroelectric properties, represents a significant development for the prospects of random-access memories.

Dynamic configurations of metallic atoms in the liquid state for selective propylene synthesis.

The use of liquid gallium as a solvent for catalytic reactions has enabled access to well-dispersed metal atoms configurations, leading to unique catalytic phenomena, including activation of neighbouring liquid atoms and mobility-induced activity enhancement. To gain mechanistic insights into liquid metal catalysts, here we introduce a GaSn0.029Ni0.023 liquid alloy for selective propylene synthesis from decane. Owing to their mobility, dispersed atoms in a Ga matrix generate configurations where interfacial Sn and Ni atoms allow for critical alignments of reactants and intermediates. Computational modelling, corroborated by experimental analyses, suggests a particular reaction mechanism by which Sn protrudes from the interface and an adjacent Ni, below the interfacial layer, aligns precisely with a decane molecule, facilitating propylene production. We then apply this reaction pathway to canola oil, attaining a propylene selectivity of ~94.5%. Our results offer a mechanistic interpretation of liquid metal catalysts with an eye to potential practical applications of this technology.

High-Performance Optoelectronic Gas Sensing Based on All-Inorganic Mixed-Halide Perovskite Nanocrystals with Halide Engineering.

Gas sensors are of great interest to portable and miniaturized sensing technologies with applications ranging from air quality monitoring to explosive detection and medical diagnostics, but the existing chemiresistive NO2 sensors still suffer from issues such as poor sensitivity, high operating temperature, and slow recovery. Herein, a high-performance NO2 sensors based on all-inorganic perovskite nanocrystals (PNCs) is reported, achieving room temperature operation with ultra-fast response and recovery time. After tailoring the halide composition, superior sensitivity of ≈67 at 8 ppm NO2 is obtained in CsPbI2 Br PNC sensors with a detection level down to 2 ppb, which outperforms other nanomaterial-based NO2 sensors. Furthermore, the remarkable optoelectronic properties of such PNCs enable dual-mode operation, i.e., chemiresistive and chemioptical sensing, presenting a new and versatile platform for advancing high-performance, point-of-care NO2 detection technologies.

Polyphenol-Mediated Liquid Metal Composite Architecture for Solar Thermoelectric Generation.

The development of advanced solar energy technologies, which efficiently convert solar energy to heat and then to electricity, remains a significant challenge in the pursuit of clean energy production. Here, this challenge is addressed by designing a photothermal absorber composed of liquid gallium particles and a natural polyphenol-based coordination ink. The design of this composite takes advantage of the tuneable light absorption properties of the polyphenol inks and can also be applied onto flexible substrates. While the ink utilizes two types of coordination complexes to absorb light at different wavelengths, the liquid gallium particles with high thermal and electrical properties provide enhanced thermoelectric effect. As such, the photothermal composite exhibits a broad-spectrum light absorption and highly efficient solar-to-heat conversion. A thermoelectric generator coated with the photothermal composite exhibits an impressive voltage output of ≈185.3 mV when exposed to 1 Sun illumination, without requiring any optical concentration, which sets a new record for a power density at 345.5 µW cm-2 . This work showcases the synergistic combination of natural compound-based light-absorbing coordination complexes with liquid metals to achieve a strong photothermal effect and their integration into thermoelectric devices with powerful light harvesting capabilities.

Passivation-Free, Liquid-Metal-Based Electrosynthesis of Aluminum Metal-Organic Frameworks Mediated by Light Metal Activation.

The production of aluminum (Al) metal-organic frameworks (MOFs) by electrosynthesis using solid-state Al electrodes always faces significant challenges due to the formation of a passivating aluminum oxide layer in the process. Here, we developed a liquid-metal-based method to electrosynthesize an aluminum Al-MOF (MIL-53). This method uses a liquid-state gallium (Ga) anode as a reservoir and activator for a light metal, Al, in the form of Al-Ga alloys that releases Al3+ for the electrosynthesis of Al-MOFs. Introducing Ga into the system inhibits the formation of aluminum oxide passivation layer and promotes the electrochemical reaction for Al-MOF synthesis. The electrosynthesis using liquid Al-Ga alloy is conducted at ambient temperatures for long durations without requiring pretreatment for aluminum oxide removal. We show that the Al-MOF products synthesized from 0.40 wt % Al in liquid Ga lead to the highest crystallinity and possess a specific surface area greater than 800 m2 g-1 and a low capacity for CO2 adsorption that can be used as a potential matrix for CO2/N2 separation. This work provides evidence that employing liquid-metal electrodes offers a viable pathway to circumvent surface passivation effects that inevitably occur when using conventional solid metals. It also introduces an efficient electrosynthesis method based on liquid metals for producing atomically porous materials.

Liquid Metal Interface for Two-Precursor Autogenous Deposition of Metal Telluride-Tellurium Networks.

Liquid metal-electrolyte can offer electrochemically reducing interfaces for the self-deposition of low-dimensional nanomaterials. We show that implementing such interfaces from multiprecursors is a promising pathway for achieving nanostructured films with combinatory properties and functionalities. Here, we explored the liquid metal-driven interfacial growth of metal tellurides using eutectic gallium-indium (EGaIn) as the liquid metal and the cation pairs Ag+-HTeO2+ and Cu2+-HTeO2+ as the precursors. At the EGaIn-electrolyte interface, the precursors were reduced and self-deposited autogenously to form interconnected nanoparticle networks. The deposited materials consisted of metal telluride and tellurium with their relative abundance depending on the metal ion type (Ag+ and Cu2+) and the metal-to-tellurium ion ratios. When used as electrode modifiers, the synthesized materials increased the electroactive surface area of unmodified electrodes by over 10 times and demonstrated remarkable activity for model electrochemical reactions, including HexRu(III) responses and dopamine sensing. Our work reveals the promising potential of the liquid metal-templated deposition method for synthesizing complex material systems for electrochemical applications.

Liquid-Metal Solvents for Designing Hierarchical Nanoporous Metals at Low Temperatures.

Metallic nanoarchitectures hold immense value as functional materials across diverse applications. However, major challenges lie in effectively engineering their hierarchical porosity while achieving scalable fabrication at low processing temperatures. Here we present a liquid-metal solvent-based method for the nanoarchitecting and transformation of solid metals. This was achieved by reacting liquid gallium with solid metals to form crystalline entities. Nanoporous features were then created by selectively removing the less noble and comparatively softer gallium from the intermetallic crystals. By controlling the crystal growth and dealloying conditions, we realized the effective tuning of the micro-/nanoscale porosities. Proof-of-concept examples were shown by applying liquid gallium to solid copper, silver, gold, palladium, and platinum, while the strategy can be extended to a wider range of metals. This metallic-solvent-based route enables low-temperature fabrication of metallic nanoarchitectures with tailored porosity. By demonstrating large-surface-area and scalable hierarchical nanoporous metals, our work addresses the pressing demand for these materials in various sectors.

Gallium Liquid Metal: Nanotoolbox for Antimicrobial Applications.

The proliferation of drug resistance in microbial pathogens poses a significant threat to human health. Hence, treatment measures are essential to surmount this growing problem. In this context, liquid metal nanoparticles are promising. Gallium, a post-transition metal notable for being a liquid at physiological temperature, has drawn attention for its distinctive properties, high antimicrobial efficacy, and low toxicity. Moreover, gallium nanoparticles demonstrate anti-inflammatory properties in immune cells. Gallium can alloy with other metals and be prepared in various composites to modify and tailor its characteristics and functionality. More importantly, the bactericidal mechanism of gallium liquid metal could sidestep the threat of emerging drug resistance mechanisms. Building on this rationale, gallium-based liquid metal nanoparticles can enable impactful and innovative strategic pathways in the battle against antimicrobial resistance. This review outlines the characteristics of gallium-based liquid metals at the nanoscale and their corresponding antimicrobial mechanisms to provide a comprehensive yet succinct overview of their current antimicrobial applications. In addition, challenges and opportunities that require further research efforts have been identified and discussed.

Detection of changes in regional colonic fermentation in response to supplementing a low FODMAP diet with dietary fibres by hydrogen concentrations, but not by luminal pH.

BACKGROUND: Carbohydrate fermentation plays a pivotal role in maintaining colonic health with excessive proximal and deficient distal fermentation being detrimental. AIMS: To utilise telemetric gas- and pH-sensing capsule technologies for defining patterns of regional fermentation following dietary manipulations, alongside conventional techniques of measuring fermentation. METHODS: In a double-blind crossover trial, 20 patients with irritable bowel syndrome were fed low FODMAP diets that included no extra fibre (total fibre content 24 g/day), or additional poorly fermented fibre, alone (33 g/day) or with fermentable fibre (45 g/day) for 2 weeks. Plasma and faecal biochemistry, luminal profiles defined by tandem gas- and pH-sensing capsules, and faecal microbiota were assessed. RESULTS: Plasma short-chain fatty acid (SCFA) concentrations (µmol/L) were median (IQR) 121 (100-222) with fibre combination compared with 66 (44-120) with poorly fermented fibre alone (p = 0.028) and 74 (55-125) control (p = 0.069), but no differences in faecal content were observed. Luminal hydrogen concentrations (%), but not pH, were higher in distal colon (mean 4.9 [95% CI: 2.2-7.5]) with fibre combination compared with 1.8 (0.8-2.8) with poorly fermented fibre alone (p = 0.003) and 1.9 (0.7-3.1) control (p = 0.003). Relative abundances of saccharolytic fermentative bacteria were generally higher in association with supplementation with the fibre combination. CONCLUSIONS: A modest increase in fermentable plus poorly fermented fibres had minor effects on faecal measures of fermentation, despite increases in plasma SCFA and abundance of fermentative bacteria, but the gas-sensing capsule, not pH-sensing capsule, detected the anticipated propagation of fermentation distally in the colon. The gas-sensing capsule technology provides unique insights into localisation of colonic fermentation. TRIAL REGISTRATION: ACTRN12619000691145.

A liquid metal-polydopamine composite for cell culture and electro-stimulation.

Gallium (Ga) is a low melting point metal in the liquid state in the biological environment which presents a unique combination of fluidity, softness, and metallic electrical and thermal properties. In this work, liquid Ga is proposed as a biocompatible electrode material for cell culture by electro-stimulation since the cytotoxicity of Ga is generally considered low and some Ga compounds have been reported to exhibit anti-bacterial and anti-inflammatory activities. Complementarily, polydopamine (PDA) was coated on liquid Ga to increase the attachment capability of cells on the liquid Ga electrode and provide enhanced biocompatibility. The liquid Ga layer could be readily painted at room temperature on a solid inert substrate, followed by the formation of a nanoscale PDA coating layer resulting in a conformable and biocompatible composite electrode. The PDA layer was shown to coordinate with Ga3+, which is sourced from liquid Ga, providing electrical conductivity in the cell culture medium. The PDA-Ga3+ composite acted as a conductive substrate for advanced electro-stimulation for cell culture methods of representative animal fibroblasts. The cell proliferation was observed to increase by ∼143% as compared to a standard glass coverslip at a low potential of 0.1 V of direct coupling stimulation. This novel PDA-Ga3+ composite has potential applications in cell culture and regenerative medicine.

Coating of gallium-based liquid metal particles with molybdenum oxide and oxysulfide for electronic band structure modulation.

Liquid metal (LM) droplets are now used in many applications including catalysis, sensing, and flexible electronics. Consequently, the introduction of methods for on-demand alternating electronic properties of LMs is necessary. The active surface of LMs provides a unique environment for spontaneous chemical reactions that enable the formation of thin layers of functional materials for such modulations. Here, we showed the deposition of n-type MoOx and MoOxSy semiconductors on the surface of EGaIn LM droplets under mechanical agitation to successfully modulate their electronic structures. The "liquid solution"-"liquid metal" interaction resulted in the formation of oxide and oxysulfide layers on the surface of LM droplets. The comprehensive study of electronic and optical properties revealed a decrease in the band gap of the droplets after surface decoration with MoOx and MoOxSy, leading to deeper n-type doping of the materials. This method provides a facile procedure for engineering the electronic band structure of LM-based composites when they are necessary for various applications.

Toward Precision Deposition of Conductive Charge-Transfer Complex Crystals Using Nanoelectrochemistry.

The lack of understanding for precise synthesis and assembly of nano-entities remains a major challenge for nanofabrication. Electrocrystallization of a charge-transfer complex (CTC), tetrathiafulvalene bromide (TTF)Br, is studied on micro/nanoelectrodes for precision deposition of functional materials. The study reveals new insights into the entire CTC electrocrystallization process from the initial nanocluster nucleation to the final elongated crystals with hollow ends grown from the working electrode to the neighboring receiving electrode. On microelectrodes, the number of nucleation sites is reduced to one by lowering the applied overpotential or precursor concentration. Certain current-time transients exhibit significant induction periods prior to stable nucleus growth. The induction regime contains small fluctuating current spikes consistent with stochastic formation of precritical nanoclusters with lifetimes of 0.1-30 s and sizes of 20-160 nm. Electrochemical analyses further reveal rate, size distribution, and formation/dissipation dynamics of the nanoclusters. Crystal growth of (TTF)Br is further studied on triangular nanoelectrode patterns with thickness of 5-500 nm, which shows a mass-transfer-controlled process applicable for precision deposition of functional (TTF)Br crystals. This study, for the first time, establishes CTC nanoelectrochemistry as a platform technology for precise deposition of conductive crystal assemblies spanning the source and drain electrode for sensing applications.

Formation of inorganic liquid gallium particle-manganese oxide composites.

Gallium (Ga) is a low melting point post-transition metal that, under mild mechanical agitation, can form micron and submicron-sized particles with combined fluid-like and metallic properties. In this work, an inorganic network of Ga liquid metal particles was synthesised via spontaneous formation of manganese (Mn) oxide species on their liquid metallic surfaces forming an all-inorganic composite. The micron-sized Ga particles formed by sonication were connected together by Mn oxide nanostructures spontaneously established from the reduction of a Mn salt in aqueous solution slightly above the melting point of Ga. The formed Mn oxide nanostructures were found to coalesce from the surface of the Ga particles into a continuous inorganic network. The morphology of the composites could be altered by varying the Mn salt concentration and by performing post-treatment annealing. The composites presented a shell of various Mn oxide nanostructures including wrinkled sheets, rods and nanoneedles, around spherical liquid Ga particles, and a liquid metal core. The photoelectric and optical properties of the composites were thoroughly characterised, which revealed decreasing bandgaps and valence band edge characteristics as a function of increased Mn oxide coverage. The photoluminescence properties of the composites could be also engineered by increasing the Mn oxide coverage. The all-inorganic liquid Ga composite could be formed via a straightforward reduction reaction of a Mn-rich salt at the surface of liquid Ga particles with tunable surface properties for future optoelectronic applications.

Mechanistic Observation of Interactions between Macrophages and Inorganic Particles with Different Densities.

Many different types of inorganic materials are processed into nano/microparticles for medical utilization. The impact of selected key characteristics of these particles, including size, shape, and surface chemistries, on biological systems, is frequently studied in clinical contexts. However, one of the most important basic characteristics of these particles, their density, is yet to be investigated. When the particles are designed for drug delivery, highly mobile macrophages are the major participants in cellular levels that process them in vivo. As such, it is essential to understand the impact of particles' densities on the mobility of macrophages. Here, inorganic particles with different densities are applied, and their interactions with macrophages studied. A set of these particles are incubated with the macrophages and the outcomes are explored by optical microscopy. This microscopic view provides the understanding of the mechanistic interactions between particles of different densities and macrophages to conclude that the particles' density can affect the migratory behaviors of macrophages: the higher the density of particles engulfed inside the macrophages, the less mobile the macrophages become. This work is a strong reminder that the density of particles cannot be neglected when they are designed to be utilized in biological applications.

Liquid metal synthesis solvents for metallic crystals.

In nature, snowflake ice crystals arrange themselves into diverse symmetrical six-sided structures. We show an analogy of this when zinc (Zn) dissolves and crystallizes in liquid gallium (Ga). The low-melting-temperature Ga is used as a "metallic solvent" to synthesize a range of flake-like Zn crystals. We extract these metallic crystals from the liquid metal solvent by reducing its surface tension using a combination of electrocapillary modulation and vacuum filtration. The liquid metal-grown crystals feature high morphological diversity and persistent symmetry. The concept is expanded to other single and binary metal solutes and Ga-based solvents, with the growth mechanisms elucidated through ab initio simulation of interfacial stability. This strategy offers general routes for creating highly crystalline, shape-controlled metallic or multimetallic fine structures from liquid metal solvents.

Liquid Metal-Templated Tin-Doped Tellurium Films for Flexible Asymmetric Pseudocapacitors.

Liquid metals can be surface activated to generate a controlled galvanic potential by immersing them in aqueous solutions. This creates energized liquid-liquid interfaces that can promote interfacial chemical reactions. Here we utilize this interfacial phenomenon of liquid metals to deposit thin films of tin-doped tellurium onto rigid and flexible substrates. This is accomplished by exposing liquid metals to a precursor solution of Sn2+ and HTeO2+ ions. The ability to paint liquid metals onto substrates enables us to fabricate supercapacitor electrodes of liquid metal films with an intimately connected surface layer of tin-doped tellurium. The tin-doped tellurium exhibits a pseudocapacitive behavior in 1.0 M Na2SO4 electrolyte and records a specific capacitance of 184.06 F·g-1 (5.74 mF·cm-2) at a scan rate of 10 mV·s-1. Flexible supercapacitor electrodes are also fabricated by painting liquid metals onto polypropylene sheets and subsequently depositing tin-doped tellurium thin films. These flexible electrodes show outstanding mechanical stability even when experiencing a complete 180° bend as well as exhibit high power and energy densities of 160 W·cm-3 and 31 mWh·cm-3, respectively. Overall, this study demonstrates the attractive features of liquid metals in creating energy storage devices and exemplifies their use as media for synthesizing electrochemically active materials.