Phase transition-driven encapsulation of biomolecules using liquid metal with on-demand release for biomedical applications.

Robust encapsulation and controllable release of biomolecules have wide biomedical applications ranging from biosensing, drug delivery to information storage. However, conventional biomolecule encapsulation strategies have limitations in complicated operations, optical instability, and difficulty in decapsulation. Here, we report a simple, robust, and solvent-free biomolecule encapsulation strategy based on gallium liquid metal featuring low-temperature phase transition, self-healing, high hermetic sealing, and intrinsic resistance to optical damage. We sandwiched the biomolecules with the solid gallium films followed by low-temperature welding of the films for direct sealing. The gallium can not only protect DNA and enzymes from various physical and chemical damages but also allow the on-demand release of biomolecules by applying vibration to break the liquid gallium. We demonstrated that a DNA-coded image file can be recovered with up to 99.9% sequence retention after an accelerated aging test. We also showed the practical applications of the controllable release of bioreagents in a one-pot RPA-CRISPR/Cas12a reaction for SARS-COV-2 screening with a low detection limit of 10 copies within 40 min. This work may facilitate the development of robust and stimuli-responsive biomolecule capsules by using low-melting metals for biotechnology.

Soft Robots with Plant-Inspired Gravitropism Based on Fluidic Liquid Metal.

Plants can autonomously adjust their growth direction based on the gravitropic response to maximize energy acquisition, despite lacking nerves and muscles. Endowing soft robots with gravitropism may facilitate the development of self-regulating systems free of electronics, but remains elusive. Herein, acceleration-regulated soft actuators are described that can respond to the gravitational field by leveraging the unique fluidity of liquid metal in its self-limiting oxide skin. The soft actuator is obtained by magnetic printing of the fluidic liquid metal heater circuit on a thermoresponsive liquid crystal elastomer. The Joule heat of the liquid metal circuit with gravity-regulated resistance can be programmed by changing the actuator's pose to induce the flow of liquid metal. The actuator can autonomously adjust its bending degree by the dynamic interaction between its thermomechanical response and gravity. A gravity-interactive soft gripper is also created with controllable grasping and releasing by rotating the actuator. Moreover, it is demonstrated that self-regulated oscillation motion can be achieved by interfacing the actuator with a monostable tape spring, allowing the electronics-free control of a bionic walker. This work paves the avenue for the development of liquid metal-based reconfigurable electronics and electronics-free soft robots that can perceive gravity or acceleration.

Breakup-Free and Colorful Liquid Metal Thin Films via Electrochemical Oxidation.

Thin-film metal conductors featuring high conductivity and stretchability are basic building blocks for high-performance conformable electronics. Gallium-based liquid metals are attractive candidates for thin-film conductors due to their intrinsic stretchability and ease of processing. Moreover, the phase change nature of liquid metal provides an opportunity to create conformal electronics in a substrate-free manner. However, thin liquid metal films tend to break during the solid-to-liquid transition due to the high surface tension of liquid metal. Here, we created breakup-free liquid metal thin films by the electrochemical oxidation of solid gallium films. We show that electrochemical oxidation can enhance the mechanical strength of the gallium oxide layer and its interfacial adhesion to the gallium core. When heated to the liquid state, the oxidized gallium films can maintain their structural integrity on various solid substrates, hydrogels, and even the water surface. The solid-liquid phase change-induced stiffness decrease allowed the gallium films to be conformably attached to various nonplanar surfaces upon heating or water transfer printing. Moreover, we also found that enhanced electrochemical oxidation can result in the formation of structure color due to nanoporous structures on the film surface. We also demonstrate the applications of oxidized liquid metal films in functional electronics, electrophysiological monitoring, and tattoo art.

Versatile sweat bioanalysis on demand with hydrogel-programmed wearables.

Wearable sweat bioanalysis is promising for non-invasive diagnostics of diseases. However, collection of representative sweat samples without disturbing daily life and wearable bioanalysis of targets that are clinically significant are still challenging. In this work, we report on a versatile method for the sweat bioanalysis. The method is based on a thermoresponsive hydrogel which can imperceptibly absorb slowly secreted sweat without stimulation such as heat or sport exercise. The wearable bioanalysis is accomplished by programmed electric heating of hydrogel modules to 42°C to release absorbed sweat or preloaded reagents into a microfluidic detection channel. Using our method, not only one-step detection of glucose but also multi-step immunoassay of cortisol is accomplished within 1 h, even at a very low sweat rate. Our test results are also compared with those obtained with conventional blood samples and stimulated sweat samples to evaluate the applicability of our method to non-invasive clinical practice.

Surface-Embedded Liquid Metal Electrodes with Abrasion Resistance via Direct Magnetic Printing.

Gallium-based liquid metals (LMs) featuring both high conductivity and fluidity are ideal conductors for soft and stretchable electronics. However, their liquid nature is a double-edged sword in many key applications since LMs are inherently prone to mechanical damage. Although additional encapsulation is frequently used for the protection of delicate LM electrodes, it hinders the electrical interfacing with other objects for interconnection, sensing, and stimulation. Here, different from conventional patterning methods that deposit LM on or inside substrates, we for the first time report a simple strategy to create surface-embedded LM of eutectic gallium-indium (EGaIn) circuits with mechanical damage endurance. This was achieved by using direct magnetic printing to overcome the high surface tension of LM, allowing it to be passively filled into the laser-patterned microgrooves on soft substrates. We show that the surface-embedded LM circuits are resistant to mechanical erasure, washing, and peeling. We also show the applications of our surface-embedded LM electrodes in respiration monitoring and electrical stimulation of nerves. This work provides a simple and efficient way to create mechanically reliable LM microelectrodes, holding great promise for wearable and implantable bioelectronics.

Ultrahigh Polarization Response along Large Energy Storage Properties in BiFeO3-BaTiO3-Based Relaxor Ferroelectric Ceramics under Low Electric Field.

BiFeO3-BaTiO3 (BF-BT) dielectric ceramics are receiving more and more concern for advanced energy storage devices owing to their excellent ferroelectric properties and environmental sustainability. However, the energy density and efficiency are limited in spite of the large remanent polarization. Herein, we proposed a multiscale optimization strategy via a local compositional disorder with a Birich content and nanodomain engineering by introducing the Sr0.7Bi0.2Ca0.1TiO3 (SBCT) into BF-BT ceramics. Interestingly, an extraordinary energy storage property (ESP) with a high reversible energy storage density (Wrec) of ∼3.79 J/cm3 and an ultrahigh polarization discrepancy (ΔP) of ∼58.5 µC/cm2 were obtained in the SBCT-modified BF-BT ceramics under 160 kV/cm. The boosted ESP should be attributed to the fact that the replacement of A/B-sites cations could transform the long-range ferroelectric order of the BF-BT system into polar nanoregions (PNRs) along with the refined grain size, decreased leakage current, and broadened energy band gap. Moreover, good frequency (1-103 Hz) and temperature (25-125 °C) stabilities, high fatigue resistance (× 105), large power density (∼31.1 MW/cm3), and fast discharge time (∼97 ns) were also observed for the optimized ceramics. These results illustrate a potentially effective method for creating high ESP lead-free ceramics at a low electric field.

Widely Targeted Metabolomics Analysis of Soybean and Chickpea and Their Different Advantages and New Functional Compounds for Diabetes.

Soybean is widely used as a kind of bean for daily consumption. Chickpea is increasingly utilised because of its good healthcare function. At present, using chickpeas could have better results than soybeans in some areas. Previous studies of the two legumes focused on certain components and failed to fully reveal the differences between the two legumes. Thus, understanding the comprehensive similarities and differences between the two legumes is necessary to apply and develop these legumes effectively. In this study, we performed a UPLC-ESI-MS/MS-based widely targeted metabolomics analysis on two legumes. A total of 776 metabolites (including primary metabolites and secondary metabolites) were detected, which were divided into more than a dozen broad categories. The differential analysis of these metabolites showed that there were 480 metabolites with significant differences in relative contents between the two legumes. Compared with soybean, the expression of 374 metabolites of chickpea was down-regulated and that of 106 metabolites was up-regulated. The metabolic pathway analysis showed significant differences in the flavonoids biosynthesis, phenylpropanoid biosynthesis, linoleic acid metabolism and alkaloid biosynthesis between the two legumes. The advantages and applicability of the two kinds of legumes were confirmed through the analysis of anti-diabetic components. Moreover, some novel compounds (with contents higher than that of soybean) with hypoglycaemic activity were found in chickpea. This study provides an important reference for the in-depth study and comparative application of soybean and chickpea.

Shape-Programmable Liquid Metal Fibers.

Conductive and stretchable fibers are the cornerstone of intelligent textiles and imperceptible electronics. Among existing fiber conductors, gallium-based liquid metals (LMs) featuring high conductivity, fluidity, and self-healing are excellent candidates for highly stretchable fibers with sensing, actuation, power generation, and interconnection functionalities. However, current LM fibers fabricated by direct injection or surface coating have a limitation in shape programmability. This hinders their applications in functional fibers with tunable electromechanical response and miniaturization. Here, we reported a simple and efficient method to create shape-programmable LM fibers using the phase transition of gallium. Gallium metal wires in the solid state can be easily shaped into a 3D helical structure, and the structure can be preserved after coating the wire with polyurethane and liquifying the metal. The 3D helical LM fiber offered enhanced stretchability with a high breaking strain of 1273% and showed invariable conductance over 283% strain. Moreover, we can reduce the fiber diameter by stretching the fiber during the solidification of polyurethane. We also demonstrated applications of the programmed fibers in self-powered strain sensing, heart rate monitoring, airflow, and humidity sensing. This work provided simple and facile ways toward functional LM fibers, which may facilitate the broad applications of LM fibers in e-skins, wearable computation, soft robots, and smart fabrics.

[EGFR tyrosine kinase inhibitor HS-10296 induces autophagy and apoptosis in triplenegative breast cancer MDA-MB-231 cells].

OBJECTIVE: To investigate the inhibitory effect of epidermal growth factor receptor tyrosine kinase inhibitor (EGFRTKI) HS-10296 on the proliferation of triple-negative breast cancer (TNBC) MDA-MB-231 cells and explore the possible molecular mechanism. METHODS: MDA-MB-231 cells were treated with HS-10296 for 24, 48, or 72 h, and CCK-8 assay was used to assess the changes in the cell viability. The inhibitory effect of HS-10296 on cell proliferation was determined by clonogenic assay. JC-1 and flow cytometry were employed for analyzing the cell apoptosis, and the ultrastructure of the cells was observed under electron microscope. After pretreatment with autophagy inhibitor chloroquine (CQ), MDA-MB-231 cells were divided into control group, CQ treatment group, HS-10296 (4 and 6 µmol/L) treatment groups and combined treatment groups, and the sensitivity of the treated cells to HS-10296 was determined using CCK-8 assay. The effects of HS-10296 on EGFR pathway and apoptosis- and autophagy-related proteins in MDA-MB-231 cells were investigated using Western blotting. RESULTS: HS-10296 significantly inhibited the proliferation of MDA-MB-231 cells with IC50 values at 24, 48 and 72 h of 8.393, 2.777 and 2.016 µmol/L, respectively. JC-1 and flow cytometry showed that HS-10296 induced obvious apoptosis of MDA-MB-231 cells, which showed an apoptosis rate of (21.63 ± 2.97)% following treatment with 8 µmol/L HS-10296. Autophagy vesicles were observed in the cells treated with HS-10296 under electron microscope. In MDA-MB-231 cells pretreated with CQ, inhibition of autophagy significantly enhanced HS-10296-induced cell death. Western blotting showed that the apoptosis-related protein caspase-3 was activated after HS-10296 treatment to cut its substrate PARP. The expression of autophagy-related protein light chain 3B (LC3B) was significantly enhanced after HS-10296 treatment (P < 0.01), which also resulted in inhibited phosphorylation of EGFR and AKT proteins in the cells. CONCLUSIONS: HS-10296 can inhibit the proliferation and induce autophagy and apoptosis of MDA-MB-231 cells by inhibiting the EGFR/PI3K/AKT signaling pathway.

Incorporation of triazacyclononane into the metal phosphonate backbones.

This paper reports the syntheses and crystal structures of a manganese and a uranyl phosphonate based on 1,4,7-triazacyclononane-1,4,7-triyl-tris(methylenephosphonic acid), namely, Mn3{C9N3H18(PO3)3}(H2O)6 x 1.5 H2O (1) and UO2{C9N3H19(PO3H)3} x H2O (2). Compound 1 shows a unique layer structure where the hydrophobic triazacyclononane moieties all reside on one side of the inorganic backbone of the manganese phosphonate layer while the hydrophilic coordinated water molecules reside on the other side. In compound 2, the triazacyclononane moieties are immobilized on the inorganic backbone of the uranyl phosphonate chains. The magnetic properties of compound 1 and the ion exchange properties of compound 2 have been studied.