Mineralization-Inspired Synthesis of Magnetic Zeolitic Imidazole Framework Composites.

Metal-organic frameworks (MOFs) capable of mobility and manipulation are attractive materials for potential applications in targeted drug delivery, catalysis, and small-scale machines. One way of rendering MOFs navigable is incorporating magnetically responsive nanostructures, which usually involve at least two preparation steps: the growth of the magnetic nanomaterial and its incorporation during the synthesis of the MOF crystals. Now, by using optimal combinations of salts and ligands, zeolitic imidazolate framework composite structures with ferrimagnetic behavior can be readily obtained via a one-step synthetic procedure, that is, without the incorporation of extrinsic magnetic components. The ferrimagnetism of the composite originates from binary oxides of iron and transition metals such as cobalt. This approach exhibits similarities to the natural mineralization of iron oxide species, as is observed in ores and in biomineralization.

Magnetoelectric Effect in Hydrogen Harvesting: Magnetic Field as a Trigger of Catalytic Reactions.

Magnetic fields have been regarded as an additional stimulus for electro- and photocatalytic reactions, but not as a direct trigger for catalytic processes. Multiferroic/magnetoelectric materials, whose electrical polarization and surface charges can be magnetically altered, are especially suitable for triggering and control of catalytic reactions solely with magnetic fields. Here, it is demonstrated that magnetic fields can be employed as an independent input energy source for hydrogen harvesting by means of the magnetoelectric effect. Composite multiferroic CoFe2 O4 -BiFeO3 core-shell nanoparticles act as catalysts for the hydrogen evolution reaction (HER), which is triggered when an alternating magnetic field is applied to an aqueous dispersion of the magnetoelectric nanocatalysts. Based on density functional calculations, it is proposed that the hydrogen evolution is driven by changes in the ferroelectric polarization direction of BiFeO3 caused by the magnetoelectric coupling. It is believed that the findings will open new avenues toward magnetically induced renewable energy harvesting.

Magnetoelectrically Driven Catalytic Degradation of Organics.

Here, the catalytic degradation of organic compounds is reported by exploiting the magnetoelectric nature of cobalt ferrite-bismuth ferrite (CFO-BFO) core-shell nanoparticles. The combination of magnetostrictive CFO with multiferroic BFO gives rise to a magnetoelectric engine that purifies water under wireless magnetic fields via advanced oxidation processes, without involvement of any sacrificial molecules or cocatalysts. Magnetostrictive CoFe2 O4 nanoparticles are fabricated using hydrothermal synthesis, followed by sol-gel synthesis to create the multiferroic BiFeO3 shell. Theoretical modeling is performed to study the magnetic-field-induced polarization on the surface of magnetoelectric nanoparticles. The results obtained from these simulations are consistent with experimental findings of the piezoforce microscopy analysis, where changes in piezoresponse of the nanoparticles under magnetic fields are observed. Next, the magnetoelectric-effect-induced catalytic degradation of organic pollutants is investigated under AC magnetic fields, and 97% removal efficiency for synthetic dyes and over 85% removal efficiency for routinely used pharmaceuticals are obtained. Additionally, trapping experiments are performed to elucidate the mechanism behind the magnetic-field-induced catalytic degradation of organic pollutants by using scavengers for each of the reactive species. The results indicate that hydroxyl and superoxide radicals are the main reactive species in the magnetoelectrically induced catalytic degradation of organic compounds.

Piezoelectrically Enhanced Photocatalysis with BiFeO3 Nanostructures for Efficient Water Remediation.

Designing new catalysts that can efficiently utilize multiple energy sources can contribute to solving the current challenges of environmental remediation and increasing energy demands. In this work, we fabricated single-crystalline BiFeO3 (BFO) nanosheets and nanowires that can successfully harness visible light and mechanical vibrations and utilize them for degradation of organic pollutants. Under visible light both BFO nanostructures displayed a relatively slow reaction rate. However, under piezocatalysis both nanosheets and nanowires exhibited higher reaction rates in comparison with photocatalytic degradation. When both solar light and mechanical vibrations were used simultaneously, the reaction rates were elevated even further, with the BFO nanowires degrading 97% of RhB dye within 1 hr (k-value 0.058 min-1). The enhanced degradation under mechanical vibrations can be attributed to the promotion of charge separation caused by the internal piezoelectric field of BFO. BFO nanowires also exhibited good reusability and versatility toward degrading four different organic pollutants.

Small-Scale Machines Driven by External Power Sources.

Micro- and nanorobots have shown great potential for applications in various fields, including minimally invasive surgery, targeted therapy, cell manipulation, environmental monitoring, and water remediation. Recent progress in the design, fabrication, and operation of these miniaturized devices has greatly enhanced their versatility. In this report, the most recent progress on the manipulation of small-scale robots based on power sources, such as magnetic fields, light, acoustic waves, electric fields, thermal energy, or combinations of these, is surveyed. The design and propulsion mechanism of micro- and nanorobots are the focus of this article. Their fabrication and applications are also briefly discussed.

Hybrid Magnetoelectric Nanowires for Nanorobotic Applications: Fabrication, Magnetoelectric Coupling, and Magnetically Assisted In Vitro Targeted Drug Delivery.

An FeGa@P(VDF-TrFE) wire-shaped magnetoelectric nanorobot is designed and fabricated to demonstrate a proof-of-concept integrated device, which features wireless locomotion and on-site triggered therapeutics with a single external power source (i.e., a magnetic field). The device can be precisely steered toward a targeted location wirelessly by rotating magnetic fields and perform on-demand magnetoelectrically assisted drug release to kill cancer cells.

Ultrasound-mediated piezoelectric differentiation of neuron-like PC12 cells on PVDF membranes.

Electrical and/or electromechanical stimulation has been shown to play a significant role in regenerating various functionalities in soft tissues, such as tendons, muscles, and nerves. In this work, we investigate the piezoelectric polymer polyvinylidene fluoride (PVDF) as a potential substrate for wireless neuronal differentiation. Piezoelectric PVDF enables generation of electrical charges on its surface upon acoustic stimulation, inducing neuritogenesis of PC12 cells. We demonstrate that the effect of pure piezoelectric stimulation on neurite generation in PC12 cells is comparable to the ones induced by neuronal growth factor (NGF). In inhibitor experiments, our results indicate that dynamic stimulation of PVDF by ultrasonic (US) waves activates calcium channels, thus inducing the generation of neurites via a cyclic adenosine monophosphate (cAMP)-dependent pathway. This mechanism is independent from the well-studied NGF induced mitogen-activated protein kinases/extracellular signal-regulated kinases (MAPK/ERK) pathway. The use of US, in combination with piezoelectric polymers, is advantageous since focused power transmission can occur deep into biological tissues, which holds great promise for the development of non-invasive neuroregenerative devices.

Multiwavelength Light-Responsive Au/B-TiO2 Janus Micromotors.

Conventional photocatalytic micromotors are limited to the use of specific wavelengths of light due to their narrow light absorption spectrum, which limits their effectiveness for applications in biomedicine and environmental remediation. We present a multiwavelength light-responsive Janus micromotor consisting of a black TiO2 microsphere asymmetrically coated with a thin Au layer. The black TiO2 microspheres exhibit absorption ranges between 300 and 800 nm. The Janus micromotors are propelled by light, both in H2O2 solutions and in pure H2O over a broad range of wavelengths including UV, blue, cyan, green, and red light. An analysis of the particles' motion shows that the motor speed decreases with increasing wavelength, which has not been previously realized. A significant increase in motor speed is observed when exploiting the entire visible light spectrum (>400 nm), suggesting a potential use of solar energy, which contains a great portion of visible light. Finally, stop-go motion is also demonstrated by controlling the visible light illumination, a necessary feature for the steerability of micro- and nanomachines.

Robotically controlled microprey to resolve initial attack modes preceding phagocytosis.

Phagocytes, predatory cells of the immune system, continuously probe their cellular microenvironment on the hunt for invaders. This requires prey recognition followed by the formation of physical contacts sufficiently stable for pickup. Although immune cells must apply physical forces to pick up their microbial prey, little is known about their hunting behavior preceding phagocytosis because of a lack of appropriate technologies. To study phagocyte hunting behavior in which the adhesive bonds by which the prey holds on to surfaces must be broken, we exploited the use of microrobotic probes to mimic bacteria. We simulate different hunting scenarios by confronting single macrophages with prey-mimicking micromagnets using a 5-degree of freedom magnetic tweezers system (5D-MTS). The energy landscape that guided the translational and rotational movement of these microparticles was dynamically adjusted to explore how translational and rotational resistive forces regulate the modes of macrophage attacks. For translational resistive prey, distinct push-pull attacks were observed. For rod-shaped, nonresistive prey, which mimic free-floating pathogens, cells co-aligned their prey with their long axis to facilitate pickup. Increasing the rotational trap stiffness to mimic resistive or surface-bound prey disrupts this realignment process. At stiffness levels on the order of 105 piconewton nanometer radian-1, macrophages failed to realign their prey, inhibiting uptake. Our 5D-MTS was used as a proof-of-concept study to probe the translational and rotational attack modes of phagocytes with high spatial and temporal resolution, although the system can also be used for a variety of other mechanobiology studies at length scales ranging from single cells to organ-on-a-chip devices.