A magnetically powered nanomachine with a DNA clutch.

Machines found in nature and human-made machines share common components, such as an engine, and an output element, such as a rotor, linked by a clutch. This clutch, as seen in biological structures such as dynein, myosin or bacterial flagellar motors, allows for temporary disengagement of the moving parts from the running engine. However, such sophistication is still challenging to achieve in artificial nanomachines. Here we present a spherical rotary nanomotor with a reversible clutch system based on precise molecular recognition of built-in DNA strands. The clutch couples and decouples the engine from the machine's rotor in response to encoded inputs such as DNA or RNA. The nanomotor comprises a porous nanocage as a spherical rotor to confine the magnetic engine particle within the nanospace (∼0.004 µm3) of the cage. Thus, the entropically driven irreversible disintegration of the magnetic engine and the spherical rotor during the disengagement process is eliminated, and an exchange of microenvironmental inputs is possible through the nanopores. Our motor is only 200 nm in size and the clutch-mediated force transmission powered by an embedded ferromagnetic nanocrystal is high enough (∼15.5 pN at 50 mT) for the in vitro mechanical activation of Notch and integrin receptors, demonstrating its potential as nano-bio machinery.

Cascade Catalytic Nanoparticles Selectively Alkalize Cancerous Lysosomes to Suppress Cancer Progression and Metastasis.

Lysosomes are critical in modulating the progression and metastasis for various cancers. There is currently an unmet need for lysosomal alkalizers that can selectively and safely alter the pH and inhibit the function of cancer lysosomes. Here an effective, selective, and safe lysosomal alkalizer is reported that can inhibit autophagy and suppress tumors in mice. The lysosomal alkalizer consists of an iron oxide core that generates hydroxyl radicals (•OH) in the presence of excessive H+ and hydrogen peroxide inside cancer lysosomes and cerium oxide satellites that capture and convert •OH into hydroxide ions. Alkalized lysosomes, which display impaired enzyme activity and autophagy, lead to cancer cell apoptosis. It is shown that the alkalizer effectively inhibits both local and systemic tumor growth and metastasis in mice. This work demonstrates that the intrinsic properties of nanoparticles can be harnessed to build effective lysosomal alkalizers that are both selective and safe.

One-Pot Heterointerfacial Metamorphosis for Synthesis and Control of Widely Varying Heterostructured Nanoparticles.

Despite remarkable facileness and potential in forming a wide variety of heterostructured nanoparticles with extraordinary compositional and structural complexity, one-pot synthesis of multicomponent heterostructures is largely limited by the lack of fundamental mechanistic understanding, designing principles, and well-established, generally applicable chemical methods. Herein, we developed a one-pot heterointerfacial metamorphosis (1HIM) method that allows heterointerfaces inside a particle to undergo multiple equilibrium stages to form a variety of highly crystalline heterostructured nanoparticles at a relatively low temperature (<100 °C). As proof-of-concept experiments, it was shown that widely different single-crystalline semiconductor-metal anisotropic nanoparticles with synergistic chemical, spectroscopic, and band-gap-engineering properties, including a series of metal-semiconductor nanoframes with high structural and compositional tunability, can be formed by using the 1HIM approach. 1HIM offers a new paradigm to synthesize previously unobtainable or poorly controllable heterostructures with unique or synergistic properties and functions.

Sensitive, Quantitative Naked-Eye Biodetection with Polyhedral Cu Nanoshells.

One of the most heavily used methods in chemical and biological labeling, detection, and imaging is based on silver shell-based enhancement on Au nanoparticles (AuNPs) that is useful for amplifying Rayleigh scattering, colorimetric signal, surface-enhanced Raman scattering, and electrical signal, but poor structural controllability and nonspecific growth of silver shells have limited its applications, especially with respect to signal reproducibility and quantification. Here, a highly specific, well-defined Cu nanopolyhedral shell overgrowth chemistry is developed with the aid of polyethyleneimine (PEI) on AuNPs, and the use of this PEI-mediated Cu polyhedral nanoshell (CuP) chemistry is shown as a means of light-scattering signal enhancement for the development of naked-eye-based highly sensitive and quantitative detections of DNA and viruses. Remarkably, these CuPs are exclusively formed on AuNPs in a controllable manner, with no noticeable nonspecific CuP growth. The findings enable to acquire clearly visible signals without analytic instrumentation, detectable down to 8 × 10-15 m of DNA (anthrax sequence) and 2700 copies of viruses (noroviruses in clinical stool samples) with broad dynamic ranges on archetypal assay platforms. This new method provides a general platform in controlling Cu shell nanostructures and their optical signals, and opens up revenues for highly reliable, quantitative onsite naked-eye biodetection.

Transformative Heterointerface Evolution and Plasmonic Tuning of Anisotropic Trimetallic Nanoparticles.

Multicomponent nanoparticles that incorporate multiple nanocrystal domains into a single particle represent an important class of material with highly tailorable structures and properties. The controlled synthesis of multicomponent NPs with 3 or more components in the desired structure, particularly anisotropic structure, and property is, however, challenging. Here, we developed a polymer and galvanic replacement reaction-based transformative heterointerface evolution (THE) method to form and tune gold-copper-silver multimetallic anisotropic nanoparticles (MAPs) with well-defined configurations, including structural order, particle and junction geometry, giving rise to extraordinarily high tunability in the structural design, synthesis and optical property of trimetallic plasmonic nanoantenna structures. MAPs can easily, flexibly integrate multiple surface plasmon resonance (SPR) peaks and incorporate various plasmonic field localization and enhancement within one structure. Importantly, a heteronanojunction in these MAPs can be finely controlled and hence tune the SPR properties of these structures, widely covering UV, visible and near-infrared range. The development of the THE method and new findings in synthesis and property tuning of multicomponent nanostructures pave ways to the fabrication of highly tailored multicomponent nanohybrids and realization of their applications in optics, energy, catalysis and biotechnology.

Growth-dissolution-regrowth transitions of Fe3O4 nanoparticles as building blocks for 3D magnetic nanoparticle clusters under hydrothermal conditions.

Magnetic nanoparticle clusters (MNCs) are a class of secondary structural materials that comprise chemically defined nanoparticles assembled into clusters of defined size. Herein, MNCs are fabricated through a one-pot solvothermal reaction featuring self-limiting assembly of building blocks and the controlled reorganization process. Such growth-dissolution-regrowth fabrication mechanism overcomes some limitations of conventional solvothermal fabrication methods with regard to restricted available feature size and structural complexity, which can be extended to other oxides (as long as one can be chelated by EDTA-2Na). Based on this method, the nanoparticle size of MNCs is tuned between 6.8 and 31.2 nm at a fixed cluster diameter of 120 nm, wherein the critical size for superparamagnetic-ferromagnetic transition is estimated from 13.5 to 15.7 nm. Control over the nature and secondary structure of MNCs gives an excellent model system to understand the nanoparticle size-dependent magnetic properties of MNCs. MNCs have potential applications in many different areas, while this work evaluates their cytotoxicity and Pb(2+) adsorption capacity as initial application study.

Poly(dopamine) coated gold nanocluster functionalized electrochemical immunosensor for brominated flame retardants using multienzyme-labeling carbon hollow nanochains as signal amplifiers.

An electrochemical, signal amplified immunosensor was developed to detect 3-bromobiphenyl (BBP) by using a bio-inspired polydopamine (PDOP)/gold nanocluster (AuNc) as the sensor platform and multienzyme-labeled carbon hollow nanochains as the signal amplifier. The self-polymerized dopamine membrane on the AuNc-modified indium tin oxide (ITO) electrode were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), contact angle and electrochemical measurements. Such PDOP/AuNc platform featured the mild cross-linking reaction with the dense immobilization of BBP-antigens (BBP-Ag). Moreover, by using multiple horseradish peroxidase (HRP) and secondary antibodies (Ab2) modified one-dimensional carbon hollow nanochains (CHNc) as the signal enhancer, it held promise for improving the sensitivity and detection limit of the immunoassay. Based on the competitive immunoassay protocol, this immunosensor showed a linear range from 1 pM to 2 nM for BBP with a detection limit of 0.5 pM. Also, it exhibited high sensitivity, wide linear range, acceptable stability and reproducibility on a promising immobilization platform using a novel signal amplifier, which may extend its application in other environmental monitoring.

High loading of uniformly dispersed Pt nanoparticles on polydopamine coated carbon nanotubes and its application in simultaneous determination of dopamine and uric acid.

Multiwalled carbon nanotubes (MWCNT) were homogeneously covered with a bio-functional polydopamine (PDOP) by a simple dip-coating approach in mild basic solution. Then, uniformly dispersed and highly loaded platinum nanoparticles (PtNPs) were deposited on MWCNT@PDOP by a mild reductant, and were characterized by transmission electron microscopy and x-ray photoelectron spectroscopy. Afterwards, this nanocomposite was modified on the glass carbon electrode and applied to simultaneously determine dopamine (DA) and uric acid (UA) by differential pulse voltammetry (DPV). Results showed that a linear electro-oxidation response was found for DA and UA in the range of 0.25-20 µM and 0.3-13 µM with the detection limit (S/N = 3) of 0.08 µM and 0.12 µM, respectively. In addition, the detection sensitivities for DA and UA by DPV were 1.03 µA µM(-1) and 2.09 µA µM(-1), respectively, which were much higher than those from a cyclic voltammogram. Finally, the reproducibility and stability of the nanocomposite were also evaluated, demonstrating that such MWCNT@PDOP@PtNPs can be a promising candidate for advanced electrode material in electrochemical sensing and other electrocatalytic applications.

Electrochemical immunoassay of benzo[a]pyrene based on dual amplification strategy of electron-accelerated Fe3O4/polyaniline platform and multi-enzyme-functionalized carbon sphere label.

An electrochemical immunosensor, basing on a dual amplification strategy by employing a biocompatible Fe(3)O(4)/polyaniline/Nafion (Fe(3)O(4)/PANI/Nafion) layer as sensor platform and multi-enzyme-antibody functionalized highly-carbonized spheres (multi-HRP-HCS-Ab(2)) as label, was constructed for sensitive detection of benzo[a]pyrene (BaP). The stable film, Fe(3)O(4)/PANI/Nafion, can not only immobilize biomolecules, but also catalyze the reduction of hydrogen peroxide, indicating an accelerated electron transfer pathway of the platform. The experimental conditions, including the concentration of Nafion, concentration of Fe(3)O(4)/polyaniline (Fe(3)O(4)/PANI), pH of the detection solution and concentrations of biomolecules, were studied in detail. Basing on a competitive immunoassay, the current change was proportional to the logarithm of BaP concentration in the range of 8 pM and 2 nM with the detection limit of 4 pM. The proposed immunosensor exhibited acceptable reproducibility and stability. This new type of dual amplification strategy may provide potential applications for the detection of environmental pollutants.

Sensitive immunosensor for benzo[a]pyrene detection based on dual amplification strategy of PAMAM dendrimer and amino-modified methylene blue/SiO2 core-shell nanoparticles.

A novel electrochemical immunosensor for sensitive detection of benzo[a]pyrene (BaP) is constructed using poly(amido amine) (PAMAM) dendrimer and functionalized methylene blue/SiO2 core-shell nanoparticle (MB/SiO2) loaded with horseradish peroxidase (HRP) and HRP-secondary antibody (HRP-Ab2). Greatly enhanced sensitivity for BaP analysis is based on a dual signal amplification strategy. Firstly, the gold electrode (GE) was amino-functioned by electropolymerization of a novel compound, 2-amino-5,2':5'2''-terthiophene, followed by the modification of G 2.0 PAMAM dendrimer to amplify functional groups on the substrate and thus enhance the immobilization capacity of BaP antigen (BaP-Ag). Secondly, amino-functionalized MB/SiO2 was used to load HRP and HRP-Ab2, and the resulting nanostructure (HRP-MB/SiO2-Ab2) was applied as the detection label for the immunosensor. The proposed immunosensor exhibited a relatively wide linear response between 0.01 and 2.0 ng/mL with a detection limit of 6 pg/mL. This amplification strategy shows excellent promise for environmental monitoring of some pollutants and a potential application in the immunosensor.