Reversed Janus Micro/Nanomotors with Internal Chemical Engine.
ABSTRACT: Self-motile Janus colloids are important for enabling a wide variety of microtechnology applications as well as for improving our understanding of the mechanisms of motion of artificial micro- and nanoswimmers. We present here micro/nanomotors which possess a reversed Janus structure of an internal catalytic "chemical engine". The catalytic material (here platinum (Pt)) is embedded within the interior of the mesoporous silica (mSiO2)-based hollow particles and triggers the decomposition of H2O2 when suspended in an aqueous peroxide (H2O2) solution. The pores/gaps at the noncatalytic (Pt) hemisphere allow the exchange of chemical species in solution between the exterior and the interior of the particle. By varying the diameter of the particles, we observed size-dependent motile behavior in the form of enhanced diffusion for 500 nm particles, and self-phoretic motion, toward the nonmetallic part, for 1.5 and 3 ?m ones. The direction of motion was rationalized by a theoretical model based on self-phoresis. For the 3 ?m particles, a change in the morphology of the porous part is observed, which is accompanied by a change in the mechanism of propulsion via bubble nucleation and ejection as well as a change in the direction of motion.
Project description:The double-faced Janus micro-motor, which utilizes the heterogeneity between its two hemispheres to generate self-propulsion, has shown great potential in water cleaning, drug delivery in micro/nanofluidics, and provision of power for a novel micro-robot. In this paper, we focus on the self-propulsion of a platinum–silica (Pt–SiO2) spherical Janus micro-motor (JM), which is one of the simplest micro-motors, suspended in a hydrogen peroxide solution (H2O2). Due to the catalytic decomposition of H2O2 on the Pt side, the JM is propelled by the established concentration gradient known as diffusoiphoretic motion. Furthermore, as the JM size increases to O (10 ?m), oxygen molecules nucleate on the Pt surface, forming microbubbles. In this case, a fast bubble propulsion is realized by the microbubble cavitation-induced jet flow. We systematically review the results of the above two distinct mechanisms: self-diffusiophoresis and microbubble propulsion. Their typical behaviors are demonstrated, based mainly on experimental observations. The theoretical description and the numerical approach are also introduced. We show that this tiny motor, though it has a very simple structure, relies on sophisticated physical principles and can be used to fulfill many novel functions.
Project description:We demonstrate a simple physical fabrication method to control surface roughness of Janus micromotors and fabricate self-propelled active Janus microparticles with rough catalytic platinum surfaces that show a four-fold increase in their propulsion speed compared to conventional Janus particles coated with a smooth Pt layer.
Project description:Mesoporous silica encapsulated Pt (Pt@mSiO2) and PtSn (PtSn@mSiO2) nanoparticles (NPs) are representatives of a novel class of heterogeneous catalysts with uniform particle size, enhanced catalytic properties, and superior thermal stability. In the ship-in-a-bottle synthesis, PtSn@mSiO2 intermetallic NPs are derived from Pt@mSiO2 seeds where the mSiO2 shell is formed by polymerization of tetraethyl orthosilicate around a tetradecyltrimethylammonium bromide template, a surfactant used to template MCM-41. Incorporation of Sn into the Pt@mSiO2 seeds is accommodated by chemical etching of the mSiO2 shell. The effect of this etching on the atomic-scale structure of the mSiO2 has not been previously examined, nor has the extent of the structural similarity to MCM-41. Here, the quaternary Q2, Q3 and Q4 sites corresponding to formulas Si(O1/2)2(OH)2, Si(O1/2)3(OH)1 and Si(O1/2)4, in MCM-41 and the mesoporous silica of Pt@mSiO2 and PtSn@mSiO2 NPs were identified and quantified by conventional and dynamic nuclear polarization enhanced Si-29 Magic Angle Spinning Nuclear Magnetic Resonance (DNP MAS NMR). The connectivity of the -Si-O-Si-network was revealed by DNP enhanced two-dimensional 29Si-29Si correlation spectroscopy.
Project description:Mg-based micromotors have emerged as an extremely attractive artificial micro/nanodevice, but suffered from uncontrollable propulsion and limited motion lifetime, restricting the fulfillment of complex tasks. Here, we have demonstrated Mg-based micromotors composed of Mg microspheres asymmetrically coated with Pt and temperature-sensitive poly(N-isopropylacrylamide) (PNIPAM) hydrogel layers in sequence. They can implement different motion behaviors stemming from the driving mechanism transformation when encountering catalyzed substrates such as H2O2 and respond to both H2O2 concentration and temperature in aqueous environment. The as-constructed Mg-based micromotors are self-propelled by Pt-catalyzed H2O2 decomposition following the self-consuming Mg-H2O reaction. In this case, they could further generate bilateral bubbles and thus demonstrate unique self-limitation motion like hovering when the phase transformation of PNIPAM is triggered by decreasing temperature or when the H2O2 concentration after permeating across the PNIPAM hydrogel layer is high enough to facilitate bubble nucleation. Our work for the first time provides a stimuli-induced "hovering" strategy for self-propelled micromotors, which endows Mg-based micromotors with an intelligent response to the surroundings besides the significant extension of their motion lifetime.
Project description:Chemically active particles achieve motility without external forces and torques ("self-propulsion") due to catalytic chemical reactions at their surfaces, which change the chemical composition of the surrounding solution (called "chemical field") and induce hydrodynamic flow of the solution. By coupling the distortions of these fields back to its motion, a chemically active particle experiences an effective interaction with confining surfaces. This coupling can lead to a rich behavior, such as the occurrence of wall-bound steady states of "sliding". Most active particles are density mismatched with the solution and, thus, tend to sediment. Moreover, the often employed Janus spheres, which consist of an inert core material decorated with a cap-like, thin layer of a catalyst, are gyrotactic (i.e., "bottom-heavy"). Whether or not they may exhibit sliding states at horizontal walls depends on the interplay between the active motion and the gravity-driven sedimentation and alignment, such as the gyrotactic tendency to align the axis along the gravity direction being overcome by a competing, activity-driven alignment with a different orientation. It is therefore important to understand and quantify the influence of these gravity-induced effects on the behavior of model chemically active particles moving in the vicinity of walls. For model gyrotactic, self-phoretic Janus particles, here we study theoretically the occurrence of sliding states at horizontal planar walls that are either below ("floor") or above ("ceiling") the particle. We construct "state diagrams" characterizing the occurrence of such states as a function of the sedimentation velocity and of the gyrotactic response of the particle, as well as of the phoretic mobility of the particle. We show that in certain cases sliding states may emerge simultaneously at both the ceiling and the floor, while the larger part of the experimentally relevant parameter space corresponds to particles that would exhibit sliding states only either at the floor or at the ceiling-or there are no sliding states at all. These predictions are critically compared with the results of previous experimental studies, as well as with our dedicated experiments carried out with Pt-coated, polystyrene-core, or silica-core Janus spheres immersed in aqueous hydrogen peroxide solutions.
Project description:Polydopamine (PDA)-a known adhesive coating material-was used herein to strongly immobilize a Pt-particle catalyst on an acrylonitrile-butadiene-styrene copolymer (ABS) substrate. Previous studies have shown that the poor adhesion between Pt particles and ABS surfaces is a considerable problem, leading to low catalytic durability for H2O2 decomposition during contact-lens cleaning. First, the ABS substrate was coated with PDA, and the PDA film was evaluated by X-ray photoelectron spectroscopy. Second, Pt particles were immobilized on the PDA-coated ABS substrate (ABS-PDA) using the electron-beam irradiation reduction method. The Pt particles immobilized on ABS-PDA (Pt/ABS-PDA) were observed using a scanning electron microscope. The Pt-loading weight was measured by inductively coupled plasma atomic emission spectroscopy. Third, the catalytic activity of the Pt/ABS-PDA was evaluated as the residual H2O2 concentration after immersing it in a 35,000-ppm H2O2 solution (the target value was less than 100 ppm). The catalytic durability was evaluated as the residual H2O2 concentration after repeated use. The PDA coating drastically improved both the catalytic activity and durability because of the high Pt-loading weight and strong adhesion among Pt particles, PDA, and the ABS substrate. Plasma treatment prior to PDA coating further improved the catalytic durability.
Project description:Motility in living systems is due to an array of complex molecular nanomotors that are essential for the function and survival of cells. These protein nanomotors operate not only despite of but also because of stochastic forces. Artificial means of realizing motility rely on local concentration or temperature gradients that are established across a particle, resulting in slip velocities at the particle surface and thus motion of the particle relative to the fluid. However, it remains unclear if these artificial motors can function at the smallest of scales, where Brownian motion dominates and no actively propelled living organisms can be found. Recently, the first reports have appeared suggesting that the swimming mechanisms of artificial structures may also apply to enzymes that are catalytically active. Here we report a scheme to realize artificial Janus nanoparticles (JNPs) with an overall size that is comparable to that of some enzymes ?30 nm. Our JNPs can catalyze the decomposition of hydrogen peroxide to water and oxygen and thus actively move by self-electrophoresis. Geometric anisotropy of the Pt-Au Janus nanoparticles permits the simultaneous observation of their translational and rotational motion by dynamic light scattering. While their dynamics is strongly influenced by Brownian rotation, the artificial Janus nanomotors show bursts of linear ballistic motion resulting in enhanced diffusion.
Project description:Unlike pressure-driven flows, surface-mediated phoretic flows provide efficient means to drive fluid motion on very small scales. Colloidal particles covered with chemically-active patches with nonzero phoretic mobility (e.g. Janus particles) swim using self-generated gradients, and similar physics can be exploited to create phoretic pumps. Here we analyse in detail the design principles of phoretic pumps and show that for a minimal phoretic pump, consisting of 3 distinct chemical patches, the optimal arrangement of the patches maximizing the flow rate is universal and independent of chemistry.
Project description:In this study, a silver doped mesoporous silica nanoparticles-based enzyme-less electrochemical sensor for the determination of hydrogen peroxide (H2O2) released from live cells was constructed for the first time. The presented electrochemical sensor exhibited fast response (2 s) towards the reduction of H2O2 concentration variation at an optimized potential of -0.5 V with high selectivity over biological interferents such as uric acid, ascorbic acid, and glucose. In addition, a wide linear range (4 μM to 10 mM) with a low detection limit (LOD) of 3 μM was obtained. Furthermore, the Ag-mSiO2 nanoparticles/glass carbon electrode (Ag-mSiO2 NPs/GCE) based enzyme-less sensor showed good electrocatalytic performance, as well as good reproducibility, and long-term stability, which provided a successful way to in situ determine H2O2 released from live cells. It may also be promising to monitor the effect of reactive oxygen species (ROS) production in bacteria against oxidants and antibiotics.
Project description:We report the construction of erythrocyte membrane-cloaked Janus polymeric motors (EM-JPMs) which are propelled by near-infrared (NIR) laser irradiation and are successfully applied in thrombus ablation. Chitosan (a natural polysaccharide with positive charge, CHI) and heparin (glycosaminoglycan with negative charge, Hep) were selected as wall materials to construct biodegradable and biocompatible capsules through the layer-by-layer self-assembly technique. By partially coating the capsule with a gold (Au) layer through sputter coating, a NIR-responsive Janus structure was obtained. Due to the asymmetric distribution of Au, a local thermal gradient was generated upon NIR irradiation, resulting in the movement of the JPMs through the self-thermophoresis effect. The reversible "on/off" motion of the JPMs and their motile behavior were easily tuned by the incident NIR laser intensity. After biointerfacing the Janus capsules with an erythrocyte membrane, the EM-JPMs displayed red blood cell related properties, which enabled them to move efficiently in relevant biological environments (cell culture, serum, and blood). Furthermore, this therapeutic platform exhibited excellent performance in ablation of thrombus through photothermal therapy. As man-made micromotors, these biohybrid EM-JPMs hold great promise of navigating in vivo for active delivery while overcoming the drawbacks of existing synthetic therapeutic platforms. We expect that this biohybrid motor has considerable potential to be widely used in the biomedical field.