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Table of contents

Volume 23

Number 7, 24 February 2012

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Papers

Biology and medicine

075101

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In this paper, the use of magnetic nanowires for the study of cellular response to force is demonstrated. High-aspect ratio Ni rods with diameter 300 nm and lengths up to 20 μm were bound to or internalized by pulmonary artery smooth muscle cells (SMCs) cultured on arrays of flexible micropost force sensors. Forces and torques were applied to the cells by driving the nanowires with AC magnetic fields in the frequency range 0.1–10 Hz, and the changes in cellular contractile forces were recorded with the microposts. These local stimulations yield global force reinforcement of the cells' traction forces, but this contractile reinforcement can be effectively suppressed upon addition of a calcium channel blocker, ruthenium red, suggesting the role of calcium channels in the mechanical response. The responsiveness of the SMCs to actuation depends on the frequency of the applied stimulation. These results show that the combination of magnetic nanoparticles and micropatterned, flexible substrates can provide new approaches to the study of cellular mechanotransduction.

075102

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Understanding the control of the optical and plasmonic properties of unique nanosystems—gold nanostars—both experimentally and theoretically permits superior design and fabrication for biomedical applications. Here, we present a new, surfactant-free synthesis method of biocompatible gold nanostars with adjustable geometry such that the plasmon band can be tuned into the near-infrared region 'tissue diagnostic window', which is most suitable for in vivo imaging. Theoretical modelling was performed for multiple-branched 3D nanostars and yielded absorption spectra in good agreement with experimental results. The plasmon band shift was attributed to variations in branch aspect ratio, and the plasmon band intensifies with increasing branch number, branch length, and overall star size. Nanostars showed an extremely strong two-photon photoluminescence (TPL) process. The TPL imaging of wheat-germ agglutinin (WGA) functionalized nanostars on BT549 breast cancer cells and of PEGylated nanostars circulating in the vasculature, examined through a dorsal window chamber in vivo in laboratory mouse studies, demonstrated that gold nanostars can serve as an efficient contrast agent for biological imaging applications.

075103

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Nanoscale drug delivery vehicles have been extensively studied as carriers for cancer chemotherapeutics. However, the formulation of platinum chemotherapeutics in nanoparticles has been a challenge arising from their physicochemical properties. There are only a few reports describing oxaliplatin nanoparticles. In this study, we derivatized the monomeric units of a polyisobutylene maleic acid copolymer with glucosamine, which chelates trans-1,2-diaminocyclohexane (DACH) platinum (II) through a novel monocarboxylato and O → Pt coordination linkage. At a specific polymer to platinum ratio, the complex self-assembled into a nanoparticle, where the polymeric units act as the leaving group, releasing DACH–platinum in a sustained pH-dependent manner. Sizing was done using dynamic light scatter and electron microscopy. The nanoparticles were evaluated for efficacy in vitro and in vivo. Biodistribution was quantified using inductively coupled plasma atomic absorption spectroscopy (ICP-AAS). The PIMA–GA–DACH–platinum nanoparticle was found to be more active than free oxaliplatin in vitro. In vivo, the nanoparticles resulted in greater tumor inhibition than oxaliplatin (equivalent to 5 mg kg−1 platinum dose) with minimal nephrotoxicity or body weight loss. ICP-AAS revealed significant preferential tumor accumulation of platinum with reduced biodistribution to the kidney or liver following PIMA–GA–DACH–platinum nanoparticle administration as compared with free oxaliplatin. These results indicate that the rational engineering of a novel polymeric nanoparticle inspired by the bioactivation of oxaliplatin results in increased antitumor potency with reduced systemic toxicity compared with the parent cytotoxic. Rational design can emerge as an exciting strategy in the synthesis of nanomedicines for cancer chemotherapy.

Electronics and photonics

075201

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Using memristive properties common for titanium dioxide thin film devices, we designed a simple write algorithm to tune device conductance at a specific bias point to 1% relative accuracy (which is roughly equivalent to seven-bit precision) within its dynamic range even in the presence of large variations in switching behavior. The high precision state is nonvolatile and the results are likely to be sustained for nanoscale memristive devices because of the inherent filamentary nature of the resistive switching. The proposed functionality of memristive devices is especially attractive for analog computing with low precision data. As one representative example we demonstrate hybrid circuitry consisting of an integrated circuit summing amplifier and two memristive devices to perform the analog multiply-and-add (dot-product) computation, which is a typical bottleneck operation in information processing.

075202

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Optically triggered UV sensitive receivers were fabricated on polycrystalline diamond as surface channel MESFETs. Opaque gates with asymmetric structure were designed in order to improve charge photogeneration mainly within the gate–drain region. Photogenerated holes contributed to the channel charge by assistance of the local electric field, in such a way improving the current signal at the drain contact. The sensitivity to UV light is demonstrated by using 3 ns wide laser pulses at 193 nm, well over the diamond bandgap. The receiver transient response to such laser pulses shows that the photogeneration process is only limited by the pulse rise time and charge collection at the drain contact completed in a time scale of a few nanoseconds. Such opaque gate three-terminal devices are suitable for application in emerging photonic technologies, for power-management system optical receivers, where copper wires and EM shielding can be replaced by lightweight optical fibers.

075203

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Nanophase semiconductors are of interest for their unique, size-tunable solar spectral absorption characteristics as well as their potential to contribute to the improved energy conversion efficiency of photovoltaics (PV). Embedding these nanoparticles within electrically active transparent conductive oxides (TCO) can also provide an opportunity for enhanced, long-range carrier transport. However, differences in the atomic and electronic structure, dielectric behavior, and chemistry between the matrix and semiconductor phases highlight the influence of interfacial effects on the optical absorption properties of the composite. In this work, nanocomposites of Ge:indium tin oxide (Ge:ITO) and Ge:ZnO were fabricated with sequential RF-magnetron sputtering and annealed at temperatures from 310 to 550 °C to investigate the impact of matrix identity on this interface and its contribution to nanostructure-mediated optical absorption. Transmission electron microscopy showed a decrease in Ge nanocrystal size relative to the initial semiconductor domain size in both matrices that was correlated with an increase in absorption onset energy after annealing. The effect was particularly pronounced in Ge:ITO composites in which Raman spectroscopy indicated the presence of germanium oxide at the semiconductor–ITO interface. These results support the primary contribution of carrier confinement in the Ge nanophase to the shifts in absorption onset energies observed.

075204

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We present a novel approach for the direct synthesis of ultrathin Si nanowires (NWs) exhibiting room temperature light emission. The synthesis is based on a wet etching process assisted by a metal thin film. The thickness-dependent morphology of the metal layer produces uncovered nanometer-size regions which act as precursor sites for NW formation. The process is cheap, fast, maskless and compatible with Si technology. Very dense arrays of long (several micrometers) and small (diameter of 5–9 nm) NWs have been synthesized. An efficient room temperature luminescence, visible with the naked eye, is observed when NWs are optically excited, exhibiting a blue-shift with decreasing NW size in agreement with quantum confinement effects. A prototype device based on Si NWs has been fabricated showing a strong and stable electroluminescence at low voltages. The relevance and the perspectives of the reported results are discussed, opening the route toward novel applications of Si NWs.

Patterning and nanofabrication

075301

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We report the fabrication of horizontally aligned ultrananocrystalline diamond (UNCD) nanowires (NWs) via two different approaches. First, with the top-down approach by using electron beam lithography (EBL) and reactive ion etching (RIE) with a photo resist layer as an etch mask. Using this approach, we demonstrate fabrication of 50 µm long UNCD NWs with widths as narrow as 40 nm. We further present an alternative approach to grow UNCD NWs at pre-defined positions through a selective seeding process. No RIE was needed either to etch the NWs or to remove the mask. In this case, we achieved UNCD NWs with lengths of 50 µm and smallest width of 90 nm respectively. Characterization of these nanowires by using scanning electron microscopy (SEM) and atomic force microscopy (AFM) shows that the UNCD NWs are well defined and fully released, with no indication of residual stress. Characterization using visible and ultraviolet (UV) Raman spectroscopy indicates that in both fabrication approaches, UNCD NWs maintain their intrinsic diamond structure.

075302

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We studied the ion beam bending of ZnO nanoneedles to find the dependence of their bending direction on the ion beam energy and to clarify the bending mechanism. Through gallium focused ion beam (FIB) bending, the stems of the nanoneedles were found to be bent to the direction of the ion beam source for ion beam energies of 30 keV whereas they were bent in the opposite direction at ion energies lower than 20 keV. We found for the first time that the bending direction of ZnO nanoneedles could be changed by repeated switching of the ion beam energy between lower and higher energy levels, and that the thin tip parts of the nanoneedles were bent toward to the ion beam source like the higher energy bending mode during the process of lower energy bending below 20 keV. Through high resolution transmission electron microscopy (HRTEM) observations of the microstructure of a nanoneedle, bent by 30 keV higher energy ion beams, based on the atomic scale, we found that more edge dislocations were created in the rear side, deeper than the central plane of the nanoneedle, than the front side and that each edge dislocation added an extra lattice plane in this region. These observations clearly showed that the bent nanoneedles were plastically deformed by the edge dislocations created by the ion beams.

075303

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In this paper, we demonstrate a distributed Bragg reflector (DBR) based on nanoporous anodic aluminum oxide (AAO) formed by pulse anodization. The AAO structure with alternating mild anodized (MA) and hard anodized (HA) layers having different porosities and thereby different refractive indices was fabricated in 0.3 M H2SO4 using potential pulses of 25 and 35 V. The effective refractive index of the HA layers can be tailored by changing the porosity of the HA layers. The porosity of the HA layers can be significantly increased by selective chemical etching of HA segments in 0.52 M H3PO4. Before etching, the porous AAO structure was supported by a polymer nanorod frame. On the selected surface area pores were infiltrated with polymers (polystyrene and PMMA). The designed AAO structure consists of alternating high and low refractive index layers and behaves as a distributed Bragg mirror reflecting light in two different ranges of wavelength. This behavior is extremely important in optical communication lines where two separate spectral bands of high reflectivity in the infrared region are desired.

Energy at the nanoscale

075401
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This paper investigates the roles of semiconducting single-walled carbon nanotubes (SWNTs) and metallic SWNTs in the SWNT/poly(3-hexylthiophene) (P3HT)-based photovoltaic conversion system. SWNTs containing different fractions of semiconducting nanotubes were conjugated with P3HT by virtue of π–π interaction. The energy transfer and carrier transport mechanisms in the photovoltaic composites were experimentally investigated by optical absorption spectroscopy, photoluminescence spectroscopy and carrier mobility measurements. At low loading of SWNTs, a high percentage of semiconducting nanotubes result in diminished non-radiative decay of exciton and lower carrier mobility, causing higher open circuit voltage and lower photocurrent. At an optimized morphology, SWNT/P3HT/phenyl-C61-butyric acid methyl ester (PCBM) hybrid-based solar cells demonstrated much higher photocurrent than a reference solar cell (P3HT:PCBM) due to the improved carrier mobility. Further thermal annealing of the devices significantly increased the open circuit voltage to 610 mV, resulting in an 80% increase of power conversion efficiency in comparison to the reference solar cell. These results are expected to lay a foundation for the integration of various nanocrystals into solar cells for efficient photovoltaic conversion.

075402

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One-dimensional flexible solar cells were fabricated through vertical growth of ZnO nanowires on freestanding carbon fibers and subsequent deposition of CdS quantum dots (QDs). Under light illumination, excitons were generated in the CdS QDs and dissociated in the ZnO/CdS interface. Photoelectrochemical characterization indicates that fiber quantum dot-sensitized solar cells (QDSCs) could effectively absorb visible light and convert it to electric energy. The photoelectrochemical performance was enhanced after the deposition of a ZnS passivating layer on the CF/ZnO/CdS surface. The highest conversion efficiency of about 0.006% was achieved by the fiber QDSCs. A higher conversion efficiency was expected to be achieved after some important parameters and cell structure were optimized and improved.

Sensing and actuating

075501

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We demonstrate a novel configuration of an electrothermal actuator (ETA), which is based on a polydimethylsiloxane (PDMS) slab sandwiched by upper and lower active layers of CNT–PDMS composite. When only one active layer of a single sandwich structure ETA is heated and the other is not, there exists a thermal gradient in the direction of the slab thickness, resulting in bending motion toward the unheated side. Moreover, a dual sandwich structure ETA, consisting of two parallel assembled sandwich structures on the same body, has the unique ability to act with a twisting motion as the two ETAs bend in opposite directions. We expect the advent of the bendable and twistable actuator to break new ground in ETAs.

Materials: synthesis or self-assembly

075601

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DNA strands have been used as templates for the self-assembly of smooth and conductive cuprous oxide (Cu2O) nanowires of diameter 12–23 nm and whose length is determined by the template (16 μm for λ-DNA). A combination of spectroscopic, diffraction and probe microscopy techniques showed that these nanowires comprise single crystallites of Cu2O bound to the DNA molecules which fused together over time in a process analogous to Ostwald ripening, but driven by the free energy of interaction with the template as well as the surface tension. Electrical characterization of the nanowires by a non-contact method, scanned conductance microscopy and by contact mode conductive AFM showed the wires are electrically conductive. The conductivity estimated from the AFM cross section and the zero-bias conductance in conductive AFM experiments was 2.2–3.3 S cm−1. These Cu2O nanowires are amongst the thinnest reported and show evidence of strong quantum confinement in electronic spectra.

Materials: properties, characterization or tools

075701

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In this work nanocomposites based on organic-capped semiconductor nanocrystals formed of a core of CdSe coated with a shell of ZnS (CdSe@ZnS), with different sizes, and a semiconducting conjugated polymer, namely poly[(9,9-dihexylfluoren-2,7-diyl)-alt- (2,5-dimethyl-1,4-phenylene)] (PF-DMB) have been investigated. The nanocomposites are prepared by mixing the pre-synthesized components in organic solvents, thereby assisting the dispersion of the organic-coated nano-objects in the polymer host. UV–vis steady state and time-resolved spectroscopy along with (photo)electrochemical techniques have been performed to characterize the obtained materials. The study shows that the embedded nanocrystals increase the PF-DMB stability against oxidation and, at the same time, extend the light harvesting capability to the visible spectral region, thus resulting in detectable photocurrent signals. The nanocomposites have been dispensed by means of a piezo-actuated inkjet system. Such inks present viscosity and surface tension properties well suited for stable and reliable drop-on-demand printing using an inkjet printer. The fabrication of arrays of single-color pixels made of the nanocomposites and micrometers in size has been performed. Confocal and atomic force microscopy have confirmed that inkjet-printed microstructures present the intrinsic emission properties of both the embedded nanocrystals and PF-DMB, resulting in a combined luminescence. Finally, the morphology of the printed pixels is influenced by the embedded nanofillers.

075702

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Thermal stability is an important property of graphene that requires thorough investigation. This study reports the thermal stability of graphene films synthesized by chemical vapor deposition (CVD) on catalytic nickel substrates in a reducing atmosphere. Electron microscopies, atomic force microscopy, and Raman spectroscopy, as well as electronic measurements, were used to determine that CVD-grown graphene films are stable up to 700 °C. At 800 °C, however, graphene films were etched by catalytic metal nanoparticles, and at 1000 °C many tortuous tubular structures were formed in the film and carbon nanotubes were formed at the film edges and at catalytic metal-contaminated sites. Furthermore, we applied our pristine and thermally treated graphene films as active channels in field-effect transistors and characterized their electrical properties. Our research shows that remnant catalytic metal impurities play a critical role in damaging graphene films at high temperatures in a reducing atmosphere: this damage should be considered in the quality control of large-area graphene films for high temperature applications.

075703

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This study describes an approach for remote measuring of on-site temperature and particle concentration using magnetic nanoparticles (MNPs) via simulation and also experimentally. The sensor model indicates that under different applied magnetic fields, the magnetization equation of the MNPs can be discretized to give a higher-order nonlinear equation in two variables that consequently separates information regarding temperature and particle concentration. As a result, on-site tissue temperature or nanoparticle concentration can be determined using remote detection of the magnetization. In order to address key issues in the higher-order equation we propose a new solution method of the first-order model from the perspective of the generalized inverse matrix. Simulations for solving the equation, as well as to optimize the solution of higher equations, were carried out. In the final section we describe a prototype experiment used to investigate the measurement of the temperature in which we used a superconducting magnetometer and commercial MNPs. The overall error after nine repeated measurements was found to be less than 0.57 K within 310–350 K, with a corresponding root mean square of less than 0.55 K. A linear relationship was also found between the estimated concentration of MNPs and the sample's mass.

075704

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Room temperature ferromagnetism has been observed in freshly synthesized and post-annealed SnO2 nanosheets. The results of x-ray diffraction and x-ray photoelectron spectroscopy reveal that the newly synthesized samples and those annealed at 400 °C under either an O2 or Ar atmosphere possess rutile structure and no other impurity phases are observed. The fitting results of the O 1s and Sn 3d spectra from SnO2 samples annealed at 400 °C under an O2 or Ar atmosphere both indicate that oxygen vacancies inevitably exist in these samples. It is found that the saturation magnetization of all the annealed samples does not feature mono-dependence on oxygen vacancies, whereas an Sn vacancy related origin seems more plausible to account for variations in the magnetization of samples studied. This finding corresponds to first-principle calculation results from our previous work. Furthermore, the Curie temperature of SnO2 nanosheets was estimated to be around 300 °C, rendering it a very good option for the next generation of spintronics.

075705

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Transmission electron microscopy (TEM) makes it possible to obtain insight into the structure, composition and reactivity of photocatalysts, which are of fundamental interest for sustainable energy research. Such insight can be used for further material optimization. Here, we combine conventional TEM analysis of photocatalysts with environmental TEM (ETEM) and photoactivation using light. Two novel types of TEM specimen holder that enable in situ illumination are developed to study light-induced phenomena in photoactive materials, systems and photocatalysts at the nanoscale under working conditions. The technological development of the holders is described and two representative photo-induced phenomena are studied: the photodegradation of Cu2O and the photodeposition of Pt onto a GaN:ZnO photocatalyst.

075706

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A series of nanostructured titanium oxide particles were synthesized by a simple wet chemical method and characterized by means of small-angle x-ray scattering (SAXS)/wide-angle x-ray scattering (WAXS), atomic force microscope (AFM), scanning electron microscope (SEM), transmission electron microscope (TEM), thermal analysis, and rheometry. Tetrabutyl titanate (TBT) and ethylene glycol (EG) can be combined to form either TiOx nanowires or smooth nanorods, and the molar ratio of TBT:EG determines which of these is obtained. Therefore, TiOx nanorods with a highly rough surface can be obtained by hydrolysis of TBT with the addition of cetyl-trimethyl-ammonium bromide (CTAB) as surfactant in an EG solution. Furthermore, TiOx nanorods with two sharp ends can be obtained by hydrolysis of TBT with the addition of salt (LiCl) in an EG solution. The AFM results show that the TiOx nanorods with rough surfaces are formed by the self-assembly of TiOx nanospheres. The electrorheological (ER) effect was investigated using a suspension of titanium oxide nanowires or nanorods dispersed in silicone oil. Oil suspensions of titanium oxide nanowires or nanorods exhibit a dramatic reorganization when submitted to a strong DC electric field and the particles aggregate to form chain-like structures along the direction of applied electric field. Two-dimensional SAXS images from chains of anisotropically shaped particles exhibit a marked asymmetry in the SAXS patterns, reflecting the preferential self-assembly of the particles in the field. The suspension of rough TiOx nanorods shows stronger ER properties than that of the other nanostructured TiOx particles. We find that the particle surface roughness plays an important role in modification of the dielectric properties and in the enhancement of the ER effect.

Comment and Reply

078001

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A recent paper (Kim et al 2010 Nanotechnology21 425102) presented results on the combination of irradiation by atomic ions of cells loaded by particles made of heavy atoms. They propose that the projectile induced x-rays emission (PIXE) mechanism has an important contribution to the enhancement of the cell death rate.

Experiments made in our group to study the effects of such a combination have shown that the Auger effect induced in the high-Z atoms and the following induction of surrounding water radiolysis has an important contribution to the enhancement of the cell death rate.

In the light of our studies we propose an alternative interpretation of the results presented in the paper by Kim et al.

078002

Upon receiving a comment (Le Sech et al 2012 Nanotechnology23 078001) on the mechanism in therapeutic effects of proton-irradiation on a tumor model given metallic nanoparticles (MNP), potential dose enhancements due to particle induced radiation (PIR) from MNP including x-ray and Auger electrons were explained, and newly termed as particle induced radiation therapy (PIRT). All other biological or chemical modulation including enhanced ROS due to PIR are also subject to further investigation. In addition, new works in this field since our original paper (Kim et al 2010 Nanotechnology21 425102) was published were briefly introduced.