Nanomotor-based biocatalytic patterning of helical metal microstructures.

A new nanomotor-based surface-patterning technique based on the movement of a magnetically powered enzyme-functionalized flexible nanowire swimmer offers the ability to create complex helical metal microstructures.

Hybrid nanomotor: a catalytically/magnetically powered adaptive nanowire swimmer.

A synthetic hybrid nanomotor, which combines chemically powered propulsion and magnetically driven locomotion, is described. The new catalytic-magnetic nanomotor consists of a flexible multisegment Pt-Au-Ag(flex)-Ni nanowire, with the Pt-Au and Au-Ag(flex)-Ni portions responsible for the catalytic and magnetic propulsion modes, respectively. The experimental data and theoretical considerations indicate that the hybrid design only minimally compromises the individual propulsion modes. Rapid and convenient switching from the catalytic to the magnetic mode is illustrated. The resulting catalytic-magnetic adaptive nanomotor can address the fuel depletion and salt limitation common to chemically powered motors by switching to magnetic propulsion. Reversal of the motion direction is also achieved upon applying the magnetic field. Such use of two sources to power a hybrid device offers a broader scope of operation and holds considerable promise for designing adaptive nanovehicles that reconfigure their operation in response to environmental changes or unexpected events.

Sensitive electrochemical detection of superoxide anion using gold nanoparticles distributed poly(methyl methacrylate)-polyaniline core-shell electrospun composite electrode.

In the present communication, a novel composite nanofibrous electrode is developed for the detection of superoxide anion (O(2)˙(-)) in phosphate buffered saline (PBS). The composite fiber electrode is fabricated by dispersing gold nanoparticles onto poly(methyl methacrylate) (PMMA)-polyaniline (PANI) core-shell electrospun nanofibers. The constructed architecture is proven to be a favorable environment for the immobilization of the enzyme, superoxide dismutase (SOD). Direct electron transfer is achieved between SOD and the electrode with an electron transfer rate constant of 8.93 s(-1). At an applied potential of +300 mV, PMMA/PANI-Au(nano)/SOD-ESCFM shows highly sensitive detection of O(2)˙(-). In addition to this, quantification of different activities of SOD is realized at PMMA/PANI-Au(nano)/SOD-ESCFM. These analytical features offer great potential for construction of the third-generation O(2)˙(-) biosensor.

Magnetically powered flexible metal nanowire motors.

Fuel-free magnetically driven propulsion of flexible Au/Ag/Ni nanowires, with a gold 'head' and nickel 'tail', linked by a partially dissolved and weakened silver bridge, is described. The flexible bridge facilitates the cyclic mechanical deformations under an external rotating magnetic field. Under such a field the nickel segment starts to rotate, facilitating the rotation of the gold segment at a different amplitude, hence breaking the system symmetry and inducing the movement. Forward ('pushing') and backward ('pulling') magnetically powered locomotion and a precise On/Off motion control are achieved by tailoring the length of the nickel and gold segments and modulating the magnetic field, respectively. Efficient locomotion in urine samples and in high-salt media is illustrated. The new magnetic nanowire swimmers can be prepared in large scale using a simple template electrodeposition protocol and offer considerable promise for diverse practical applications.

Motion-based DNA detection using catalytic nanomotors.

Synthetic nanomotors, which convert chemical energy into autonomous motion, hold considerable promise for diverse applications. In this paper, we show the use of synthetic nanomotors for detecting DNA and bacterial ribosomal RNA in a fast, simple and sensitive manner. The new motion-driven DNA-sensing concept relies on measuring changes in the speed of unmodified catalytic nanomotors induced by the dissolution of silver nanoparticle tags captured in a sandwich DNA hybridization assay. The concentration-dependent distance signals are visualized using optical microscopy, particularly through straight-line traces by magnetically aligned 'racing' nanomotors. This nanomotor biodetection strategy could be extended to monitor a wide range of biomolecular interactions using different motion transduction schemes, thus providing a versatile and powerful tool for detecting biological targets.

Nanomotor-based 'writing' of surface microstructures.

This communication demonstrates the 'writing' of surface microstructures by localized material deposition through the predefined movement of enzyme modified catalytic nanomotors.

Template-assisted fabrication of salt-independent catalytic tubular microengines.

A simplified template-assisted layering approach for preparing catalytic conical tube microjet engines based on sequential deposition of platinum and gold on an etched silver wire template followed by dicing and dissolution of the template is described. The method allows detailed control over the tube parameters and hence upon the performance of the microengine. The recoiling bubble propulsion mechanism of the tubular microengine, associated with the ejection of internally generated oxygen microbubbles, addresses the ionic-strength limitation of catalytic nanowire motors and leads to a salt-independent movement. Similar rates of bubble generation and motor speeds are observed in salt-free and salt-rich media (at elevated ionic-strength environments as high as 1 M NaCl). Plating of an intermediate nickel layer facilitates a magnetically guided motion as well as the pickup and transport of large (magnetic) "cargo". Surfactant addition is shown to decrease the surface tension and offer a more frequent formation of dense smaller bubbles. The new and improved motor capabilities along with the simple preparation route hold great promise for using catalytic micromotors in diverse and important applications.

Motion control at the nanoscale.

Synthetic nanoscale motors represent a major step in the development of practical nanomachines. This Review summarizes recent progress towards controlling the movement of fuel-driven nanomotors and discusses the challenges and opportunities associated with the achievement of such nanoscale motion control. Regulating the movement of artificial nanomotors often follows nature's elegant and remarkable approach for motion control. Such on-demand control of the movement of artificial nanomotors is essential for performing various tasks and diverse applications. These applications require precise control of the nanomotor direction as well as temporal and spatial regulation of the motor speed. Different approaches for controlling the motion of catalytic nanomotors have been developed recently, including magnetic guidance, thermally driven acceleration, an electrochemical switch, and chemical stimuli (including control of the fuel concentration). Such ability to control the directionality of artificial nanomotors and to regulate their speed offers considerable promise for designing powerful nanomachines capable of operating independently and meeting a wide variety of future technological needs.

Chemical sensing based on catalytic nanomotors: motion-based detection of trace silver.

A motion-based chemical sensing involving fuel-driven nanomotors is demonstrated. The new protocol relies on the use of an optical microscope for tracking changes in the speed of nanowire motors in the presence of the target analyte. Selective and sensitive measurements of trace silver ions are illustrated based on the dramatic and specific acceleration of bimetal nanowire motors in the presence of silver. Such nanomotor-based measurements would lead to a wide range of novel and powerful chemical and biological sensing protocols.

Electrochemically-triggered motion of catalytic nanomotors.

An electrochemically-controlled movement of catalytic nanomotors, including a cyclic 'on/off' activation of the nanomotor motion and a fine speed control, is illustrated.

Enzyme logic gates for the digital analysis of physiological level upon injury.

A biocomputing system composed of a combination of AND/IDENTITY logic gates based on the concerted operation of three enzymes: lactate oxidase, horseradish peroxidase and glucose dehydrogenase was designed to process biochemical information related to pathophysiological conditions originating from various injuries. Three biochemical markers: lactate, norepinephrine and glucose were applied as input signals to activate the enzyme logic system. Physiologically normal concentrations of the markers were selected as logic 0 values of the input signals, while their abnormally increased concentrations, indicative of various injury conditions were defined as logic 1 input. Biochemical processing of different patterns of the biomarkers resulted in the formation of norepiquinone and NADH defined as the output signals. Optical and electrochemical means were used to follow the formation of the output signals for eight different combinations of three input signals. The enzymatically processed biochemical information presented in the form of a logic truth table allowed distinguishing the difference between normal physiological conditions, pathophysiological conditions corresponding to traumatic brain injury and hemorrhagic shock, and abnormal situations (not corresponding to injury). The developed system represents a biocomputing logic system applied for the analysis of biomedical conditions related to various injuries. We anticipate that such biochemical logic gates will facilitate decision-making in connection to an integrated therapeutic feedback-loop system and hence will revolutionize the monitoring and treatment of injured civilians and soldiers.

Fabrication and properties of poly(vinylidenefluoride)/PbS/Au heterogeneous nanostructures.

We report on the fabrication of polyvinylidenefluoride (PVdF) PVdF/PbS and PVdF/PbS/Au heterogeneous nanostructures by the processes, electrospinning and chemical treatment. Initially electrospinning a solution consisting of PVdF and lead acetate was used to form PVdF nanofibers loaded with Pb ions. Exposure of Pb ions loaded PVdF fibers to H2S resulted in PVdF/PbS nanostructures. The deposition of gold nanoparticles onto PVdF/PbS nanostructures results in PVdF/PbS/Au heterogeneous structure. The existence of PbS particles with an average diameter of 11 nm is evident from field emission transmission electron microscopy (FETEM) image of PVdF/PbS. The results from X-ray diffraction of PVdF/PbS also predict the size of PbS particles as in accordance with FETEM. A blue shift in the optical transition of PbS is noticed in the UV-visible spectrum of PVdF/PbS as a result of quantum confinement effect. The band gap of PbS is influenced by the presence of Au nanoparticles over the PbS particles. An equal atomic weight % of Au and PbS is found in the PVdF/PbS/Au nanostructure as inferred from energy dispersive X-ray spectroscopy (EDX). Photoluminescence (PL) spectra of PVdF/PbS and PVdF/PbS/Au are compared. Emission peaks are noticed at 400 nm and 480 nm for PVdF/PbS and PVdF/PbS/Au nanostructures respectively for an excitation wavelength of 254 nm. The presence of Au nanoclusters in PVdF/PbS/Au diminishes the intensity of photo emission of PbS.

Synthesis and characterization of nanostructured wires (1D) to plates (3D) LiV3O8 combining sol-gel and electrospinning processes.

Using the combined techniques of sol-gel and electrospinning, nanostructures (wire (1D) to plates (3D)) of LiV3O8 are prepared with poly vinyl alcohol (PVA) as the template. A precursor gel of LiOH-V2O5 is prepared in alkaline medium. Fibrous membranes of PVA with different weight% of LiOH-V2O5 gel are prepared by electrospinning and designated as PVA/LiOH-V2O5 composite membrane fibers. The composite fibrous membranes are subjected to calcination at 500 degrees C to obtain different nanostructured LiV3O8. FESEM images of LiV3O8 inform that as the loading % of LiOH-V2O5 gel in the composite membrane increased, the morphology of LiV3O8 changed from fibrous wires (1D) to plates (3D). FESEM images reveal that the diameters of the composite fibrous membranes, PVA/LiOH-V2O5 are in the range of 80-120 nm. Results from X-ray diffraction and thermal studies clearly confirm the formation of LiV3O8 after calcination of PVA/LiOH-V2O5 composite membrane at 500 degrees C. It is presumed that this preparation strategy can be extended to obtain nanostructures of other inorganic oxides.

Thermal modulation of nanomotor movement.

Motion control is essential for various applications of man-made nanomachines. The ability to control and regulate the movement of catalytic nanowire motors is illustrated by applying short heat pulses that allow the motors to be accelerated or slowed down. The accelerated motion observed during the heat pulses is attributed primarily to the thermal activation of the redox reactions of the H(2)O(2) fuel at the Pt and Au segments and to the decreased viscosity of the aqueous medium at elevated temperatures. The thermally modulated motion during repetitive temperature on/off cycles is highly reversible and fast, with speeds of 14 and 45 microm s(-1) at 25 and 65 degrees C, respectively. A wide range of speeds can be generated by tailoring the temperature to yield a linear speed-temperature dependence. Through the use of nickel-containing nanomotors, the ability to combine the thermally regulated motion of catalytic nanomotors with magnetic guidance is also demonstrated. Such on-demand control of the movement of nanowire motors holds great promise for complex operations of future manmade nanomachines and for creating more sophisticated nanomotors.

Electrochemical detection of celecoxib at a polyaniline grafted multiwall carbon nanotubes modified electrode.

A modified electrode is fabricated by grafting polyaniline (PANI) chains onto multiwall carbon nanotubes (MWNTs) and utilized for the adsorptive reduction of celecoxib (CEL). PANI-g-MWNTs modified electrode appreciably enhances the sensitive detection of CEL in extremely lower concentrations (1x10(-11)M). Square wave stripping voltammogram (SWSV) shows a reduction peak at -1.08V with a high peak current for SW frequency of 100Hz, amplitude of 25mV and step height of 6mV. The high surface area of PANI-g-MWNTs is effectively utilized for the adsorption of CEL to preconcentrate at the electrode. The PANI chains covalently linked to MWNTs mediate the electron transfer processes. The present finding open-up the scope for extending on the use of other conducting polymers grafted MWNTs modified electrodes for the detection of compounds that do not have surface-active properties at conventional electrodes.

Electrochemical determination of dopamine and ascorbic acid at a novel gold nanoparticles distributed poly(4-aminothiophenol) modified electrode.

A modified electrode is fabricated by embedding gold nanoparticles into a layer of electroactive polymer, poly(4-aminothiophenol) (PAT) on the surface of glassy carbon (GC) electrode. Cyclic voltammetry (CV) is performed to deposit PAT and concomitantly deposit Au nanoparticles. Field emission transmission electron microscopic image of the modified electrode, PAT-Au(nano)-ME, indicates the presence of uniformly distributed Au nanoparticles having the sizes of 8-10nm. Electrochemical behavior of the PAT-Au(nano)-ME towards detection of ascorbic acid (AA) and dopamine (DA) is studied using CV. Electrocatalytic determination of DA in the presence of fixed concentration of AA and vice versa, are studied using differential pulse voltammetry (DPV). PAT-Au(nano)-ME exhibits two well defined anodic peaks at the potential of 75 and 400mV for the oxidation of AA and DA, respectively with a potential difference of 325mV. Further, the simultaneous determination of AA and DA is studied by varying the concentration of AA and DA. PAT-Au(nano)-ME exhibits selectivity and sensitivity for the simultaneous determination of AA and DA without fouling by the oxidation products of AA or DA. PAT and Au nanoparticles provide synergic influence on the accurate electrochemical determination of AA or DA from a mixture having any one of the component (AA or DA) in excess. The practical analytical utilities of the PAT-Au(nano)-ME are demonstrated by the determination of DA and AA in dopamine hydrochloride injection and human blood serum samples.

Fabrication and electrocatalysis of self-assembly directed gold nanoparticles anchored carbon nanotubes modified electrode.

A self-assembly directed approach was adopted to modify glassy carbon electrode (GC) with gold nanoparticles incorporation and the electrocatalytic performance of self-assembly modified electrode, GC/SA-Au-ME was critically evaluated for the oxidation of ascorbic acid (AA). The modification involves the dispersion of multi-wall carbon nanotube (MWNT) and an inclusion complex, beta-cyclodextrin-4-aminothiophenol on the surface of GC electrode in the presence of cetyltrimethylammonium bromide (CTAB). Gold nanoparticles were deposited into the self-assembled sites to fabricate the modified electrode, GC/SA-Au-ME. Another electrode (GC-Au-ME) was fabricated under similar conditions in the absence of CTAB. The electrocatalytic activity of the modified electrodes (GC/SA-Au-ME and GC-Au-ME) towards the oxidation of AA was critically compared. Cyclic voltammetry, chronoamperometry, and double potential chronoamperometry were used to evaluate the characteristics of the modified electrodes. The self-assembled electrode (GC/SA-Au-ME) shows excellent electrocatalytic activity over the other electrode, GC-Au-ME. Augmented current response, faster electron transfer kinetics (with a rate constant for electron transfer process as 3.25 x 10(4) cm3 mol(-1) s(-1)), linear range of response for the analyte (1-50 mM with an extended detection limit to 1 microM), better sensitivity, and selectivity were witnessed for the self-assembly directed modified electrode.

Nanostructuring of poly(diphenylamine) inside the galleries of montmorillonite organo clay through self-assembly approach.

Hollow spheres of poly(diphenylamine) (PDPA) was prepared by confining PDPA in the galleries of montmorillonite organo clay modified with organoammonium cations (MMT). At first instant, diphenylamine (DPA) was loaded into the galleries of MMT and subjected to subsequent oxidative polymerization to form PDPA. beta-naphthalene sulfonic acid (NSA) was used as medium to influence self-assembly of DPA inside the galleries of MMT. Polymerization of self assembled structure resulted hollow spheres of PDPA inside galleries of MMT. X-ray diffraction analysis (XRD), field emission transmission electron microscopy (FETEM), Fourier transform infra-red spectroscopy (FT-IR) and thermogravimetric analysis (TGA) were used to characterize the composites. Transmission emission microscopy of the composite shows the hollow spherical morphology of PDPA. FT-IR, UV-Visible spectroscopy, conductivity measurement and X-ray photoelectron spectroscopy were used to characterize the PDPA extracted from MMT galleries. PDPA extracted from MMT galleries was found to have difference in electronic property than PDPA formed by the conventional method, due to the confinement effect.