Dissolution-driven propulsion of floating solids.

We show that unconstrained asymmetric dissolving solids floating in a fluid can move rectilinearly as a result of attached density currents which occur along their inclined surfaces. Solids in the form of boats composed of centimeter-scale sugar and salt slabs attached to a buoy are observed to move rapidly in water with speeds up to 5 mm/s determined by the inclination angle and orientation of the dissolving surfaces. While symmetric boats drift slowly, asymmetric boats are observed to accelerate rapidly along a line before reaching a terminal velocity when their drag matches the thrust generated by dissolution. By visualizing the flow around the body, we show that the boat velocity is always directed opposite to the horizontal component of the density current. We derive the thrust acting on the body from its measured kinematics and show that the propulsion mechanism is consistent with the unbalanced momentum generated by the attached density current. We obtain an analytical formula for the body speed depending on geometry and material properties and show that it captures the observed trends reasonably. Our analysis shows that the gravity current sets the scale of the body speed consistent with our observations, and we estimate that speeds can grow slowly as the cube root of the length of the inclined dissolving surface. The dynamics of dissolving solids demonstrated here applies equally well to solids undergoing phase change and may enhance the drift of melting icebergs, besides unraveling a primal strategy by which to achieve locomotion in active matter.

Multifunctional Chiral Chemically-Powered Micropropellers for Cargo Transport and Manipulation.

Practical applications of synthetic self-propelled nano and microparticles for microrobotics, targeted drug delivery, and manipulation at the nanoscale are rapidly expanding. However, fabrication limitations often hinder progress, resulting in relatively simple shapes and limited functionality. Here, taking advantage of 3D nanoscale printing, chiral micropropellers powered by the hydrogen peroxide reduction reaction are fabricated. Due to their chirality, the propellers exhibit multifunctional behavior controlled by an applied magnetic field: spinning in place (loitering), directed migration in the prescribed direction, capture, and transport of polymer cargo particles. Design parameters of the propellers are optimized by computation modeling based on mesoscale molecular dynamics. It is predicted by computer simulations, and confirmed experimentally, that clockwise rotating propellers attract each other and counterclockwise repel. These results shed light on how chirality and shape optimization enhance the functionality of synthetic autonomous micromachines.

Enzymatic Nanomotors Surviving Harsh Conditions Enabled by Metal Organic Frameworks Encapsulation.

Enzyme-driven micro/nanomotors (MNMs) have demonstrated potentials in the biomedical field because of their excellent biocompatibility, versatility, and fuel bioavailability. However, the fragility of enzymes limits their practical application, because of their susceptibility to denaturation and degradation in realistic scenarios. Herein, a simple yet versatile and effective approach is reported to preserve the enzymatic activity and propulsion capability of enzymatic MNMs under various harsh conditions using metal organic frameworks (MOFs) as a protective shell. Urease can be encapsulated within the exoskeleton of zeolitic imidazolate framework-8 (ZIF-8) via biomimetic mineralization to form ZIF-8@urease (ZU-I) nanomotors that exhibit self-propulsion in the presence of urea. When exposed to harsh conditions, including high temperature, presence of proteases, and organic solvents, the ZU-I nanomotors still maintained their activity and mobility, whereas ZIF-8 with externally modified urease (ZU-O) nanomotors with externally modified urease as a control rapidly lost their motion capabilities owing to the inactivation of urease. Furthermore, ZU-I nanomotors exhibit effectively enhanced diffusion within the small intestine fluid, achieving a fourfold higher mucus penetration than the ZU-O nanomotors. The results highlight the effectiveness of using MOFs as protective shells for enzyme nano-engines, which can greatly advance the practical applications of enzymatic MNMs under realistic conditions, especially for biomedical purpose.

Field-Directed Motion, Cargo Capture, and Closed-Loop Controlled Navigation of Microellipsoids.

Microrobots have the potential for diverse applications, including targeted drug delivery and minimally invasive surgery. Despite advancements in microrobot design and actuation strategies, achieving precise control over their motion remains challenging due to the dominance of viscous drag, system disturbances, physicochemical heterogeneities, and stochastic Brownian forces. Here, a precise control over the interfacial motion of model microellipsoids is demonstrated using time-varying rotating magnetic fields. The impacts of microellipsoid aspect ratio, field characteristics, and magnetic properties of the medium and the particle on the motion are investigated. The role of mobile micro-vortices generated is highlighted by rotating microellipsoids in capturing, transporting, and releasing cargo objects. Furthermore, an approach is presented for controlled navigation through mazes based on real-time particle and obstacle sensing, path planning, and magnetic field actuation without human intervention. The study introduces a mechanism of directing motion of microparticles using rotating magnetic fields, and a control scheme for precise navigation and delivery of micron-sized cargo using simple microellipsoids as microbots.

Mechanisms of transport enhancement for self-propelled nanoswimmers in a porous matrix.

Micro/nanoswimmers convert diverse energy sources into directional movement, demonstrating significant promise for biomedical and environmental applications, many of which involve complex, tortuous, or crowded environments. Here, we investigated the transport behavior of self-propelled catalytic Janus particles in a complex interconnected porous void space, where the rate-determining step involves the escape from a cavity and translocation through holes to adjacent cavities. Surprisingly, self-propelled nanoswimmers escaped from cavities more than 20× faster than passive (Brownian) particles, despite the fact that the mobility of nanoswimmers was less than 2× greater than that of passive particles in unconfined bulk liquid. Combining experimental measurements, Monte Carlo simulations, and theoretical calculations, we found that the escape of nanoswimmers was enhanced by nuanced secondary effects of self-propulsion which were amplified in confined environments. In particular, active escape was facilitated by anomalously rapid confined short-time mobility, highly efficient surface-mediated searching for holes, and the effective abolition of entropic and/or electrostatic barriers at the exit hole regions by propulsion forces. The latter mechanism converted the escape process from barrier-limited to search-limited. These findings provide general and important insights into micro/nanoswimmer mobility in complex environments.

Recent Advances in Light-Driven Semiconductor-Based Micro/Nanomotors: Optimization Strategies and Emerging Applications.

Micro/nanomotors represent a burgeoning field of research featuring small devices capable of autonomous movement in liquid environments through catalytic reactions and/or external stimuli. This review delves into recent advancements in light-driven semiconductor-based micro/nanomotors (LDSM), focusing on optimized syntheses, enhanced motion mechanisms, and emerging applications in the environmental and biomedical domains. The survey commences with a theoretical introduction to micromotors and their propulsion mechanisms, followed by an exploration of commonly studied LDSM, emphasizing their advantages. Critical properties affecting propulsion, such as surface features, morphology, and size, are presented alongside discussions on external conditions related to light sources and intensity, which are crucial for optimizing the propulsion speed. Each property is accompanied by a theoretical background and conclusions drawn up to 2018. The review further investigates recent adaptations of LDSM, uncovering underlying mechanisms and associated benefits. A brief discussion is included on potential synergistic effects between different external conditions, aiming to enhance efficiency-a relatively underexplored topic. In conclusion, the review outlines emerging applications in biomedicine and environmental monitoring/remediation resulting from recent LDSM research, highlighting the growing significance of this field. The comprehensive exploration of LDSM advancements provides valuable insights for researchers and practitioners seeking to leverage these innovative micro/nanomotors in diverse applications.

Supramolecular Modular Assembly of Imaging-Trackable Enzymatic Nanomotors.

Self-propelled micro/nanomotors (MNMs) have shown great application potential in biomedicine, sensing, environmental remediation, etc. In the past decade, various strategies or technologies have been used to prepare and functionalize MNMs. However, the current preparation strategies of the MNMs were mainly following the pre-designed methods based on specific tasks to introduce expected functional parts on the various micro/nanocarriers, which lacks a universal platform and common features, making it difficult to apply to different application scenarios. Here, we have developed a modular assembly strategy based on host-guest chemistry, which enables the on-demand construction of imaging-trackable nanomotors mounted with suitable driving and imaging modules using a universal assembly platform, according to different application scenarios. These assembled nanomotors exhibited enhanced diffusion behavior driven by enzymatic reactions. The loaded imaging functions were used to dynamically trace the swarm motion behavior of assembled nanomotors with corresponding fuel conditions both in vitro and in vivo. The modular assembly strategy endowed with host-guest interaction provides a universal approach to producing multifunctional MNMs in a facile and controllable manner, which paves the way for the future development of MNMs systems with programmable functions.

ON-OFF Control of Marangoni Self-propulsion via A Supra-amphiphile Fuel and Switch.

Marangoni self-propulsion refers to motion of liquid or solid driven by a surface tension gradient, and has applications in soft robots/devices, cargo delivery, self-assembly etc. However, two problems remain to be addressed for motion control (e.g., ON-OFF) with conventional surfactants as Marangoni fuel: (1) limited motion lifetime due to saturated interfacial adsorption of surfactants; (2) in- situ motion stop is difficult once Marangoni flows are triggered. Instead of covalent surfactants, supra-amphiphiles with hydrophilic and hydrophobic parts linked noncovalently, hold promise to solve these problems owing to its dynamic and reversible surface activity responsively. Here, we propose a new concept of 'supra-amphiphile fuel and switch' based on the facile synthesis of disodium-4-azobenzene-amino-1,3-benzenedisulfonate (DABS) linked by a Schiff base, which has amphiphilicity for self-propulsion, hydrolyzes timely to avoid saturated adsorption, and provides pH-responsive control over ON-OFF motion. The self-propulsion lifetime is extended by 50-fold with DABS and motion control is achieved. The mechanism is revealed with coupled interface chemistry involving two competitive processes of interfacial adsorption and hydrolysis of DABS based on both experiments and simulation. The concept of 'supra-amphiphile fuel and switch' provides an active solution to prolong and control Marangoni self-propulsive devices for the advance of intelligent material systems.

Magnetically Driven Self-Degrading Zinc-Containing Cystine Microrobots for Treatment of Prostate Cancer.

Prostate cancer is the most commonly diagnosed tumor disease in men, and its treatment is still a big challenge in standard oncology therapy. Magnetically actuated microrobots represent the most promising technology in modern nanomedicine, offering the advantage of wireless guidance, effective cell penetration, and non-invasive actuation. Here, new biodegradable magnetically actuated zinc/cystine-based microrobots for in situ treatment of prostate cancer cells are reported. The microrobots are fabricated via metal-ion-mediated self-assembly of the amino acid cystine encapsulating superparamagnetic Fe3 O4 nanoparticles (NPs) during the synthesis, which allows their precise manipulation by a rotating magnetic field. Inside the cells, the typical enzymatic reducing environment favors the disassembly of the aminoacidic chemical structure due to the cleavage of cystine disulfide bonds and disruption of non-covalent interactions with the metal ions, as demonstrated by in vitro experiments with reduced nicotinamide adenine dinucleotide (NADH). In this way, the cystine microrobots served for site-specific delivery of Zn2+ ions responsible for tumor cell killing via a "Trojan horse effect". This work presents a new concept of cell internalization exploiting robotic systems' self-degradation, proposing a step forward in non-invasive cancer therapy.

Engineered Organic Nanorockets with Light-Driven Ultrafast Transportability for Antitumor Therapy.

Nanomedicines confront various complicated physiological barriers limiting the accumulation and deep penetration in the tumor microenvironment, which seriously restricts the efficacy of antitumor therapy. Self-propelled nanocarriers assembled with kinetic engines can translate external energy into orientated motion for tumor penetration. However, achieving a stable ultrafast permeability at the tumor site remains challenging. Here, sub-200 nm photoactivated completely organic nanorockets (NRs), with asymmetric geometry conveniently assembled from photothermal semiconducting polymer payload and thermo-driven macromolecular propulsion through a straightforward nanoprecipitation process, are presented. The artificial NRs can be remotely manipulated by 808 nm near-infrared light to trigger the photothermal conversion and Curtius rearrangement reaction within the particles for robustly pushing nitrogen out into the solution. Such a two-stage light-to-heat-to-chemical energy transition effectively powers the NRs for an ultrafast (≈300 µm s-1 ) and chemical medium-independent self-propulsion in the liquid media. That endows the NRs with high permeability against physiological barriers in the tumor microenvironment to directionally deliver therapeutic agents to target lesions for elevating tumor accumulation, deep penetration, and cellular uptake, resulting in a significant enhancement of antitumor efficacy. This work will inspire the design of advanced kinetic systems for powering intelligent nanomachines in biomedical applications.

A Hydrolyzable Supra-amphiphile as a Marangoni Self-Propulsion Fuel for Efficient Macroscopic Supramolecular Self-Assembly.

Self-assembly of µm-to-mm components is important for achieving all-scale ordering with requirements of extra energy for motion and interaction of components. Marangoni flows caused by surfactants on water provide appropriate energy but have limited lifetimes because of the inevitable interfacial aggregation and difficult decomposition of aggregated covalent surfactants that inactivate Marangoni effects. Here we have synthesized a supra-amphiphile Marangoni "fuel"-sodium-4-(benzylideneamino) benzenesulfonate (SBBS)-that can be hydrolyzed in a timely manner to a species without surface activity to extend the motion time by 10-fold. The motion was optimized at pH=2 by a fine equilibrium between the releasing and removal of interfacial SBBS, leading to the self-assembly of millimeter-scaled ordered dimers. The underlying mechanism was interpreted by motion analyses and simulation. This strategy provides an active solution to self-assembly at the µm-to-mm scale, as well as interactive ideas between miniaturized chemical robots.

Photoactivated Organic Nanomachines for Programmable Enhancement of Antitumor Efficacy.

Limited permeability in solid tumors significantly restricts the anticancer efficacy of nanomedicines. Light-driven nanomotors powered by photothermal converting engines are appealing carriers for directional drug delivery and simultaneous phototherapy. Nowadays, it is still a great challenge to construct metal-free photothermal nanomotors for a programmable anticancer treatment. Herein, one kind of photoactivated organic nanomachines is reported with asymmetric geometry assembled by light-to-heat converting semiconducting polymer engine and macromolecular anticancer payload through a straightforward nanoprecipitation process. The NIR-fueled polymer engine can be remotely controlled to power the nanomachines for light-driven thermophoresis in the liquid media and simultaneously thermal ablating the cancer cells. The great manipulability of the nanomachines allows for programming of their self-propulsion in the tumor microenvironment for effectively improving cellular uptake and tumor penetration of the anticancer payload. Taking the benefit from this behavior, a programmed treatment process is established at a low drug dose and a low photothermal temperature for significantly enhancing the antitumor efficacy.

A Chemotactic Colloidal Motor.

Chemotaxis plays a crucial role in the realization of various functions of human life such as fertilization, immune function, inflammatory response, regeneration processes, etc. Inspired by the natural chemotaxis, colloidal motors with chemotactic ability can realize intelligent sense and targeted navigation, which bring a revolutionary method to biomedical applications like precision medicine. However, the application in the biomedical field requires the colloidal motors with submicrometer scale, strong chemotactic ability and clear chemotactic mechanism. In this Concept article, we introduce the recent progress of chemotactic colloidal motors, covering the fundamental theory behind experimental advancements. Particularly, the torque-driven reorientation motion of the submicrometer-sized colloidal motors during chemotaxis is discussed, and also their underlying mechanism is proposed. With the continuous research on chemotactic colloidal motors, it is believed that the emerging chemotactic colloidal motors will broaden practical applications in the biomedical field.

Self-propulsion of inverse Leidenfrost drops on a cryogenic bath.

When deposited on a hot bath, volatile drops are observed to stay in levitation: the so-called Leidenfrost effect. Here, we discuss drop dynamics in an inverse Leidenfrost situation where room-temperature drops are deposited on a liquid-nitrogen pool and levitate on a vapor film generated by evaporation of the bath. In the seconds following deposition, we observe that the droplets start to glide on the bath along a straight path, only disrupted by elastic bouncing close to the edges of the container. Initially at rest, these self-propelled drops accelerate within a few seconds and reach velocities on the order of a few centimeters per second before slowing down on a longer time scale. They remain self-propelled as long as they are sitting on the bath, even after freezing and cooling down to liquid-nitrogen temperature. We experimentally investigate the parameters that affect liquid motion and propose a model, based on the experimentally and numerically observed (stable) symmetry breaking within the vapor film that supports the drop. When the film thickness and the cooling dynamics of the drops are also modeled, the variations of the drop velocities can be accurately reproduced.

Torque-Driven Orientation Motion of Chemotactic Colloidal Motors.

We report a direct experimental observation of the torque-driven active reorientation of glucose-fueled flasklike colloidal motors to a glucose gradient exhibiting a positive chemotaxis. These streamlined flasklike colloidal motors are prepared by combining a hydrothermal synthesis and a vacuum infusion and can be propelled by an enzymatic cascade reaction in the glucose fuel. Their flasklike architecture can be used to recognize their moving posture, and thus the dynamic glucose-gradient-induced alignment and orientation-dependent motility during positive chemotaxis can be examined experimentally. The chemotactic mechanism is that the enzymatic reactions inside lead to the glucose acid gradient and the glucose gradient which generate two phoretic torques at the bottom and the opening respectively, and thus continuously steer it to the glucose gradient. Such glucose-fueled flasklike colloidal motors resembling the chemotactic capability of living organisms hold considerable potential for engineering active delivery vehicles in response to specific chemical signals.

Autonomous Chiral Microswimmers with Self-mixing Capabilities for Highly Efficient Enantioselective Synthesis.

The development of chiral catalysts plays a very important role in various areas of chemical science. Heterogeneous catalysts have the general advantage of allowing a more straightforward separation from the products. One specific case of heterogeneous catalysis is electrocatalysis, being potentially a green chemistry approach. However, a typical drawback is that the redox conversion of molecules occurs only at the electrode/electrolyte interface, and not in the bulk of the electrolyte. The second limitation is that the electrodes have to be physically connected to a power supply to induce the desired reactions. To circumvent these problems, we propose here a complementary approach by replacing macroscopic electrodes with an ensemble of self-propelled redox active microswimmers. They move autonomously in solution while transforming simultaneously a prochiral starting compound into a specific enantiomer with a very high enantiomeric excess, accompanied by a significantly increased production rate of the favorite enantiomer.

Self-Propelling Hybrid Gels Incorporating an Active Self-Assembled, Low-Molecular-Weight Gelator.

Hybrid gel beads based on combining a low-molecular-weight gelator (LMWG) with a polymer gelator (PG) demonstrate an enhanced ability to self-propel in water, with the LMWG playing an active role. Hybrid gel beads were loaded with ethanol and shown to move in water owing to the Marangoni effect changes in surface tension caused by the expulsion of ethanol - smaller beads move farther and faster than larger beads. Flat shapes of the hybrid gel were cut using a "stamp" - circles moved the furthest, whereas stars showed more rotation on their own axes. Comparing hybrid LMWG/PG gel beads with PG-only beads demonstrated that the LMWG speeds up the beads, enhancing the rate of self-propulsion. Self-assembly of the LMWG into a "solid-like" network prevents its leaching from the gel. The LMWG also retains its own unique function - specifically, remediating methylene blue pollutant dye from basic water as a result of noncovalent interactions. The mobile hybrid beads accumulate this dye more effectively than PG-only beads. Self-propelling gel beads have potential applications in removal/delivery of active agents in environmental or biological settings. The ability of self-assembling LMWGs to enhance mobility and control removal/delivery suggests that adding them to self-propelling systems can add significant value.

Self-Propelled Active Photothermal Nanoswimmer for Deep-Layered Elimination of Biofilm In Vivo.

Increasing penetration of antibacterial agents into biofilm is a promising strategy for improvement of therapeutic effect and slowdown of the progression of antibiotic resistance. Herein, we design a near-infrared (NIR) light-driven nanoswimmer (HSMV). Under NIR light irradiation, HSMV performs efficient self-propulsion and penetrates into the biofilm within 5 min due to photothermal conversion of asymmetrically distributed AuNPs. The localized thermal (∼45 °C) and thermal-triggered release of vancomycin (Van) leads to an efficient combination of photothermal therapy and chemotherapy in one system. The active motion of HSMV increases the effective distance of photothermal therapy (PTT) and also improves the therapeutic index of the antibiotic, resulting in superior biofilm removal rate (>90%) in vitro. Notably, HSMV can eliminate S. aureus biofilms grown in vivo under 10 min of laser irradiation without damage to healthy tissues. This work may shed light on therapeutic strategies for in vivo treatment of biofilm-associated infections.

Bubble-Propelled Janus Gallium/Zinc Micromotors for the Active Treatment of Bacterial Infections.

We report a bubble-propelled Janus gallium/zinc (Ga/Zn) micromotor with good biocompatibility and biodegradability for active target treatment of bacteria. The Janus Ga/Zn micromotors are fabricated by asymmetrically coating liquid metal Ga on Zn microparticles and display self-propulsion in simulated gastroenteric acid (pH 0.5) at a speed of up to 383 µm s-1 , propelled by hydrogen bubbles generated by the zinc-acid reaction. This motion of Ga/Zn micromotors is enhanced by the Ga-Zn galvanic effect. The GaIII cations produced from the degradation of Ga/Zn micromotors serve as a built-in antibiotic agent. The movement improves the diffusion of GaIII and results in a significant increase of the antibacterial efficiency against H. pylori, compared with passive Ga microparticles. Such Ga/Zn micromotors combine the self-propulsion, good biocompatibility and biodegradability, and Ga-based antibacterial properties, providing a proof of concept for the active treatment of bacterial infections.

Programmable Dynamic Shapes with a Swarm of Light-Powered Colloidal Motors.

We report robust control over the dynamic assembly, disassembly, and reconfiguration of light-activated molybdenum disulfide (MoS2 ) colloidal motor swarms with features not possible in equilibrium systems. A photochemical reaction produces chemical gradients across the MoS2 colloidal motors to drive them to move. Under illumination of a gradient light, these colloidal motors display a positive phototactic motion. Mesoscale simulations prove that the self-diffusiophoresis induced by the locally consumed oxygen gradient across MoS2 colloidal motors dominates the phototactic process. By programming the structured illumination, the collective migration and well-defined shapes of colloidal motor swarms can be externally regulated. The successful realization of programmable swarm transformation of colloidal motors like the emergent behaviors of living systems in nature provides a direct proof-of-concept for active soft materials and systems, with adaptive and interactive functions.