Colloidal synthesis of metallodielectric Janus matchsticks.

We present a gram-scale synthesis of metallodielectric Janus matchsticks, which feature a gold-coated silica sphere and a silica rod. SiO2 Janus matchsticks are synthesized in one batch by growing amine-functionalized SiO2 spheres at the end of SiO2 rods. Gold deposition on the spheres produces Au-SiO2 Janus matchsticks with an aspect ratio controlled by the rod length. The metallodielectric Janus matchsticks, produced by scalable colloidal synthesis, hold great potential as functional colloidal materials.

Biomimetic thermoresponsive superstructures by colloidal soft-and-hard co-assembly.

Soft-and-hard hybrid structures are ubiquitous in biological systems and have inspired the design of man-made mechanical devices, actuators, and robots. The realization of these structures, however, has been challenging at microscale, where material integration and actuation become exceedingly less practical. Here, through simple colloidal assembly, we create microscale superstructures consisting of soft and hard materials, which, serving as microactuators, have thermoresponsive shape-transforming properties. In this case, anisotropic metal-organic framework (MOF) particles as the hard components are integrated with liquid droplets, forming spine-mimicking colloidal chains via valence-limited assembly. The chains, with alternating soft and hard segments, are referred to as MicroSpine and can reversibly change shape, switching between straight and curved states through a thermoresponsive swelling/deswelling mechanism. By solidification of the liquid parts within a chain with prescribed patterns, we design various chain morphologies, such as "colloidal arms," with controlled actuating behaviors. The chains are further used to build colloidal capsules, which encapsulate and release guests by the temperature-programmed actuation.

Light-Activated Colloidal Micromotors with Synthetically Tunable Shapes and Shape-Directed Propulsion.

Controlling the propulsion modes of colloidal micromotors, from translational to spinning and helical motion, expands the versatility of their potential applications in microrobotics and micromachinery. Engineering colloidal shapes with designed asymmetry can regulate their propulsion behaviors, yet current methods rely on complicated and costly fabrication processes such as lithography. Herein, we present a solution-based synthesis of light-activated colloidal motors adopting straight and various tunable bent geometries, which feature controlled asymmetry and allow shape-directed propulsions. The keys for our strategy are the synthesis of bent silica rods with a tailored bending position and degree, together with the site-specific installation of a photoactive engine. Upon light illumination, the resulting particles propel autonomously, whereby their shape information is translated to various propulsion modes including linear locomotion, steering, and spinning. This low-cost, scalable method for fabricating micromotors with a high degree of control of shapes could promote study in microscale actuation, in active assembly, and eventually for fabrication of colloidal functional materials.

Boosting cisplatin chemotherapy by nanomotor-enhanced tumor penetration and DNA adducts formation.

Despite many nano-based strategies devoted to delivering cisplatin for tumor therapy, its clinical benefits are compromised by poor tissue penetration and limited DNA adducts formation of the drug. Herein, a cisplatin loading nanomotor based janus structured Ag-polymer is developed for cisplatin delivery of deeper tissue and increased DNA adducts formation. The nanomotor displayed a self-propelled tumor penetration fueled by hydrogen peroxide (H2O2) in tumor tissues, which is catalytically decomposed into a large amount of oxygen bubbles by Ag nanoparticles (NPs). Notably, cisplatin could elevate the intracellular H2O2 level through cascade reactions, further promote the degradation of Ag NPs accompanied with the Ag+ release, which could downregulate intracellular Cl- through the formation of AgCl precipitate, thereby enhancing cisplatin dechlorination and Pt-DNA formation. Moreover, polymer can also inhibit the activity of ALKBH2 (a Fe2+-dependent DNA repair enzyme) by chelating intracellular Fe2+ to increase the proportion of irreparable Pt-DNA cross-links. It is found that deep tissue penetration, as well as the increased formation and maintenance of Pt-DNA adducts induced by the nanomotor afford 80% of tumor growth inhibition with negligible toxicity. This work provides an important perspective of resolving chemotherapeutic barriers for boosting cisplatin therapy.

Binary Phases and Crystals Assembled from Active and Passive Colloids.

Classic binary materials, ranging from polymer blends to table salts, contain equilibrium phases or crystals of two interacting components. Here, we report on the construction of binary colloidal materials out of equilibrium by employing active particles and passive particles that dynamically interact and organize. Key to our scheme is the introduction of photoactive microspheres whose activity can be precisely tuned. This allows us to leverage the complex nonequilibrium interplay between the constituent components for dynamic coassembly. A wide variety of binary structures have thus been realized, including the liquid-crystal phases and crystal-crystal phases via phase separation and, counterintuitively, the binary crystalline compounds. The obtained structures are validated by computer simulations, which reveal unexpected kinetic pathways that are unique for active systems. With these findings, our strategy could facilitate the design and fabrication of multicomponent materials beyond equilibrium.

Pharmacological inhibition of Kv1.3 channel impairs TLR3/4 activation and type I IFN response and confers protection against Listeria monocytogenes infection.

Emerging data have demonstrated the critical roles of potassium efflux in the innate immune system. However, the role of potassium efflux in TLR3/4 activation and type I interferon (IFN) responses are not well elucidated. In the present study, we found potassium efflux is essential for TLR3/4 signaling, which mediates the expression of IFN and its inducible gene Cxcl10 and proinflammatory cytokine gene TNF-α. Furthermore, pharmacological inhibition of Kv1.3 channel (PAP-1), but not Kir2.1, KCa3.1 or TWIK2, attenuated TLR3/4 receptor activation in macrophages. Mechanistically, PAP-1 suppressed LPS-induced inflammatory function through marked suppressing the activation of JNK mitogen-activated protein kinase (MAPK) and p65 subunit of nuclear factor-kB (NF-kB). Notably, PAP-1 effectively protected mice against Listeria monocytogenes induced infection. Our findings reveal that potassium efflux mediated by the Kv1.3 channel is essential for TLR3/4 activation and suggest that pharmacological inhibition of Kv1.3 may help to treat type I IFN related autoimmune diseases and bacterial infections.

Polyhedral Micromotors of Metal-Organic Frameworks: Symmetry Breaking and Propulsion.

Colloidal micromotors can autonomously propel due to their broken symmetry that leads to unbalanced local mechanical forces. Most commonly, micromotors are synthesized to possess a Janus structure or its variants, having two components distinct in shape, composition, or surface joined together on opposite sides. Here, we report on an alternative approach for creating micromotors, where microcrystals of metal-organic frameworks (MOFs) with various polyhedral shapes are propelled under an AC electric field. In these cases, symmetry breaking is realized by orienting the polyhedral particles in a unique direction to generate uneven electrohydrodynamic flow. The particle orientations are controlled by a delicate competition between the electric and gravitational forces exerted on the particle, which we rationalize using experiments and a theoretical model. Furthermore, by leveraging the MOF types and shapes, or surface properties, we show that the propulsion of MOF motors can be tuned or reversed. Because of the flexibility in designing MOFs and their one-step scalable synthesis, our strategy is simple yet versatile for making well-defined functional micromotors.

NaH Promoted One-Pot Tandem Reactions of 3-(1-Alkynyl) Chromones to Form 2-Nitrogen-Substituted Xanthones.

A silver-catalyzed dimerization of ethyl isocyanoacetates could trigger the tandem reaction of 3-(1-alkynyl) chromones under the basic condition in a one-pot reaction to afford xanthone skeletons with 2-imidazolyl substitution in an efficient manner. With the control experiment in hand, a mechanism including dimerization of isocyanoacetate/deprotonation/Michael addition/ring-opening/cyclization 1,2-elimination was deduced. Further investigation for the base was carried out, resulting in NaH as an optimal base to avoid the dimerization of 3-(1-alkynyl) chromones. The scope of this methodology was extended on the different substituents of 3-(1-alkynyl)-chromones and the potential of other N-heterocycle glycine ester anions to give the novel functional 2-nitrogen-derived xanthones.

Phoretic Liquid Metal Micro/Nanomotors as Intelligent Filler for Targeted Microwelding.

Micro/nanomotors (MNMs) have emerged as active micro/nanoplatforms that can move and perform functions at small scales. Much of their success, however, hinges on the use of functional properties of new materials. Liquid metals (LMs), due to their good electrical conductivity, biocompatibility, and flexibility, have attracted considerable attentions in the fields of flexible electronics, biomedicine, and soft robotics. The design and construction of LM-based motors is therefore a research topic with tremendous prospects, however current approaches are mostly limited to macroscales. Here, the fabrication of an LM-MNM (made of Galinstan, a gallium-indium-tin alloy) is reported and its potential application as an on-demand, self-targeting welding filler is demonstrated. These LM-MNMs (as small as a few hundred nanometers) are half-coated with a thin layer of platinum (Pt) and move in H2 O2 via self-electrophoresis. In addition, the LM-MNMs roaming in a silver nanowire network can move along the nanowires and accumulate at the contact junctions where they become fluidic and achieve junction microwelding at room temperature by reacting with acid vapor. This work presents an intelligent and soft nanorobot capable of repairing circuits by welding at small scales, thus extending the pool of available self-propelled MNMs and introducing new applications.

Base-Promoted Cascade Reactions of 3-(1-Alkynyl)chromones with Pyridinium Ylides to Chromeno[2,3- d]azepine Derivatives.

A base-promoted cascade reaction of 3-(1-alkynyl)chromones with pyridinium ylides has been developed to afford a novel chromeno[2,3- d]azepine scaffold in an efficient and economic manner. This tandem process involves multiple reactions including a Michael addition/deprotonation/alkyne-allene isomerization/cyclization and the subsequent 1,2-addition under mild conditions without a transition metal catalyst.

Paper-Based Versatile Surface-Enhanced Raman Spectroscopy Chip with Smartphone-Based Raman Analyzer for Point-of-Care Application.

With the advanced development of miniaturized Raman spectroscopy, surface-enhanced Raman spectroscopy (SERS) has extended its applications into the field of point-of-care testing (POCT) and demonstrated its great significance by virtue of its noninvasive property and capability of fingerprint identification. In the SERS-based analysis and/or sensing system, the preparation of a low-cost, high-performance SERS substrate is critically important. In this manuscript, vacuum filtration is utilized to fabricate the silver nanoparticles (AgNPs)-embedded nylon filter membrane (ANFM) as flexible paper-based SERS chips. By characterizing the typical analytes with a miniaturized smartphone-based Raman analyzer, the proposed SERS chips have successfully demonstrated good sensitivity, repeatability, and stability. The lowest concentration as detected can approach 1 pmol for rhodamine 6G (RH6G) and 10 pmol for both crystal violet (CV) and malachite green (MG), respectively. With the help of the microporous structure of the membrane, the ANFM-based SERS chips can implement the separation of small molecules from a complex mixture and can achieve "purified" SERS signals of targeted molecules. Besides, with the function of antifriction resistance and flexibility, the ANFM can serve as SERS papers to preconcentrate the contaminates by multiple swapping and further enhance the SERS signals for point-of-care analysis. Therefore, we demonstrate multifunctions of the flexible ANFM-based SERS chips, which provide a promising solution for the POCT analysis with the SERS technique on account of their flexibility and low fabrication cost.