To date, numerous inorganic nanocarriers have been explored for drug delivery systems (DDSs). However, the clinical application of inorganic formulations has often been hindered by their toxicity and failure to biodegrade. We describe here a transformable liquid-metal nanomedicine, based on a core–shell nanosphere composed of a liquid-phase eutectic gallium-indium core and a thiolated polymeric shell. This formulation can be simply produced through a sonication-mediated method with bioconjugation flexibility. The resulting nanoparticles loaded with doxorubicin (Dox) have an average diameter of 107 nm and demonstrate the capability to fuse and subsequently degrade under a mildly acidic condition, which facilitates release of Dox in acidic endosomes after cellular internalization. Equipped with hyaluronic acid, a tumour-targeting ligand, this formulation displays enhanced chemotherapeutic inhibition towards the xenograft tumour-bearing mice. This liquid metal-based DDS with fusible and degradable behaviour under physiological conditions provides a new strategy for engineering theranostic agents with low toxicity.
Soft conductors are created by embedding liquid metal nanoparticles between two elastomeric sheets. Initially, the particles form an electrically insulating composite. Soft circuit boards can be handwritten by a stylus, which sinters the particles into conductive traces by applying localized mechanical pressure to the elastomeric sheets. Antennas with tunable frequencies are formed by sintering nanoparticles in microchannels.
This work discusses the attributes, fabrication methods, and applications of gallium‐based liquid metal particles. Gallium‐based liquid metals combine metallic and fluidic properties at room temperature. Unlike mercury, which is toxic and has a finite vapor pressure, gallium possesses low toxicity and effectively zero vapor pressure at room temperature, which makes it amenable to many applications. A variety of fabrication methods produce liquid metal particles with variable sizes, ranging from nm to mm (which is the upper limit set by the capillary length). The liquid nature of gallium enables fabrication methods—such as microfluidics and sonication—that are not possible with solid materials. Gallium‐based liquid metal particles possess several notable attributes, including a metal–metal oxide (liquid–solid) core–shell structure as well as the ability to self‐heal, merge, and change shape. They also have unusual phase behavior that depends on the size of the particles. The particles have no known commercial applications, but they show promise for drug delivery, soft electronics, microfluidics, catalysis, batteries, energy harvesting, and composites. Existing challenges and future opportunities are discussed herein.
This paper reports the formation of shape-changing and phase-transforming liquid metal particles that have potential applications in drug delivery, catalysis, colloidal jamming, and optics.
Effective endosomal escape remains as the "holy grail" for endocytosis-based intracellular drug delivery. To date, most of the endosomal escape strategies rely on small molecules, cationic polymers, or pore-forming proteins, which are often limited by the systemic toxicity and lack of specificity. We describe here a light-fueled liquid-metal transformer for effective endosomal escape-facilitated cargo delivery via a chemical-mechanical process. The nanoscale transformer can be prepared by a simple approach of sonicating a low-toxicity liquid-metal. When coated with graphene quantum dots (GQDs), the resulting nanospheres demonstrate the ability to absorb and convert photoenergy to drive the simultaneous phase separation and morphological transformation of the inner liquid-metal core. The morphological transformation from nanospheres to hollow nanorods with a remarkable change of aspect ratio can physically disrupt the endosomal membrane to promote endosomal escape of payloads. This metal-based nanotransformer equipped with GQDs provides a new strategy for facilitating effective endosomal escape to achieve spatiotemporally controlled drug delivery with enhanced efficacy.
1605630(1 of 8) temperature, and low viscosity. The latter property allows LM to flow in response to deformation, whereas solid metals are stiff and prone to fail at small strains. Embedding LM in elastomer decouples the electrical and mechanical properties; that is, these composites have the electrical properties of the metal and the mechanical properties of the elastomer. Incorporating the LM into the hollow core of an elastomeric fiber results in a useful form for sensors because fibers may be integrated into clothing and fabrics. [12][13][14][15] Furthermore, fibers are inherently flexible, compliant, and conformal due to their narrow cross-section. Thus, fibers can readily wrap onto and conform to surfaces with Gaussian curvature whereas 2D sheets cannot without significant deformation. Fibers can also be mass produced at high speeds with small diameters (hundreds of microns) and produced by hand in a laboratory environment at room temperature. [16] The fibers described in this work have the additional advantage of being built from stretchable and soft materials. Fibers with LM cores have previously been used to make light-emitting structures [17] and stretchable wires that retain metallic conductance up to ≈800% strain. [18] We reasoned that elastomeric fibers filled with LM could also be used for capacitive sensing of torsion, strain, and touch.Here, we intertwined two fibers into a double-helix to create sensors of both torsion and strain since twisting or stretching the fibers increases the contact area between them, and therefore changes the capacitance. The complexity of torsion, which causes both normal and shear strain, has previously precluded the development of a simple sensor capable of measuring a large range of torsion. Existing torsion sensors measure changes in normalized resistance, [2,8,19,20] pressure, [9] and optical properties, [21] or utilize surface acoustic waves [22] or the inverse magnetostrictive effect. [23] Some of these sensors can detect changes as small as 0.3 rad m −1 and can measure torsion up to 800 rad m −1 before failure. Most existing torsion sensors, however, are rigid, cumbersome, expensive, and complex. The soft and stretchable sensor developed here offers a simple mechanism to measure large changes in torsion which may be useful for unconventional robotics [24,25] or artificial muscles. [26] In addition to sensing torsion, intertwined fibers increase capacitance in response to strain due to the increase in contact Soft and stretchable sensors have the potential to be incorporated into soft robotics and conformal electronics. Liquid metals represent a promising class of materials for creating these sensors because they can undergo large deformations while retaining electrical continuity. Incorporating liquid metal into hollow elastomeric capillaries results in fibers that can integrate with textiles, comply with complex surfaces, and be mass produced at high speeds. Liquid metal is injected into the core of hollow and extremely stretchable elastomeric fibers and the re...
This paper describes the utilization of vacuum to fill complex microchannels with liquid metal. Microchannels filled with liquid metal are useful as conductors for soft and stretchable electronics, as well as for microfluidic components such as electrodes, antennas, pumps, or heaters. Liquid metals are often injected manually into the inlet of a microchannel using a syringe. Injection can only occur if displaced air in the channels has a pathway to escape, which is usually accomplished using outlets. The positive pressure (relative to atmosphere) needed to inject fluids can also cause leaks or delamination of the channels during injection. Here we show a simple and hands-free method to fill microchannels with liquid metal that addresses these issues. The process begins by covering a single inlet with liquid metal. Placing the entire structure in a vacuum chamber removes the air from the channels and the surrounding elastomer. Restoring atmospheric pressure in the chamber creates a positive pressure differential that pushes the metal into the channels. Experiments and a simple model of the filling process both suggest that the elastomeric channel walls absorb residual air displaced by the metal as it fills the channels. Thus, the metal can fill dead-ends with features as small as several microns and branched structures within seconds without the need for any outlets. The method can also fill completely serpentine microchannels up to a few meters in length. The ability to fill dense and complex geometries with liquid metal in this manner may enable broader application of liquid metals in electronic and microfluidic applications.
Rapid room-temperature synthesis of metal-organic frameworks (MOFs) is highly desired for industrial implementation and commercialization. Here we find that a (Zn,Cu) hydroxy double salt (HDS) intermediate formed in situ from ZnO particles or thin films enables rapid growth (<1 min) of HKUST-1 (Cu3(BTC)2) at room temperature. The space-time-yield reaches >3 × 10(4) kg·m(-3)·d(-1), at least 1 order of magnitude greater than any prior report. The high anion exchange rate of (Zn,Cu) hydroxy nitrate HDS drives the ultrafast MOF formation. Similarly, we obtained Cu-BDC, ZIF-8, and IRMOF-3 structures from HDSs, demonstrating synthetic generality. Using ZnO thin films deposited via atomic layer deposition, MOF patterns are obtained on pre-patterned surfaces, and dense HKUST-1 coatings are grown onto various form factors, including polymer spheres, silicon wafers, and fibers. Breakthrough tests show that the MOF-functionalized fibers have high adsorption capacity for toxic gases. This rapid synthesis route is also promising for new MOF-based composite materials and applications.
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