Table of contents

Volume 22

Number 19, 13 May 2011

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Papers

Biology and medicine

195101

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Carbon nanotube substrates are promising candidates for biological applications and devices. Interfacing of these carbon nanotubes with neurons can be controlled by chemical modifications. In this study, we investigated how chemical surface functionalization of multi-walled carbon nanotube arrays (MWNT-A) influences neuronal adhesion and network organization. Functionalization of MWNT-A dramatically modifies the length of neurite fascicles, cluster inter-connection success rate, and the percentage of neurites that escape from the clusters. We propose that chemical functionalization represents a method of choice for developing applications in which neuronal patterning on MWNT-A substrates is required.

195102

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Molecular imaging enables the non-invasive investigation of cellular and molecular processes. Although there are challenges to overcome, the development of targeted contrast agents to increase the sensitivity of molecular imaging techniques is essential for their clinical translation. In this study, spontaneously forming, small unilamellar vesicles (sULVs) (30 nm diameter) were used as a platform to build a bimodal (i.e., optical and magnetic resonance imaging (MRI)) targeted contrast agent for the molecular imaging of brain tumors. sULVs were loaded with a gadolinium (Gd) chelated lipid (Gd-DPTA-BOA), functionalized with targeting antibodies (anti-EGFR monoclonal and anti-IGFBP7 single domain), and incorporated a near infrared dye (Cy5.5). The resultant sULVs were characterized in vitro using small angle neutron scattering (SANS), phantom MRI and dynamic light scattering (DLS). Antibody targeted and nontargeted Gd loaded sULVs labeled with Cy5.5 were assessed in vivo in a brain tumor model in mice using time domain optical imaging and MRI. The results demonstrated that a spontaneously forming, nanosized ULVs loaded with a high payload of Gd can selectively target and image, using MR and optical imaging, brain tumor vessels when functionalized with anti-IGFBP7 single domain antibodies. The unique features of these targeted sULVs make them promising molecular MRI contrast agents.

Electronics and photonics

195201

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We investigated capacitors based on polycrystalline narrow-band-gap BiFeO3 (BFO) thin films with different top electrodes. The photovoltaic response for the capacitor with a Sn-doped In2O3 (ITO) top electrode is about 25 times higher than that with a Au top electrode, which indicates that the electrode plays a key role in determining the photovoltaic response of ferroelectric thin film capacitors, as simulated by Qin et al (2009 Appl. Phys. Lett.95 22912). The light-to-electricity photovoltaic efficiency for the ITO/polycrystalline BFO/Pt capacitor can reach 0.125%. Furthermore, under incident light of 450 µW cm − 2 and zero bias, the corresponding photocurrent varies from 0.2 to 200 pA, that is, almost a 1000-fold photoconductivity enhancement. Our experiments suggest that polycrystalline BFO films are promising materials for application in photo-sensitive and energy-related devices.

195202

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The electrical properties of carbon nanotube thin-film transistors (CNT–FETs) fabricated using plasma-enhanced chemical vapor deposition (PECVD) were studied by scanning probe microscopy. The measured results suggest the formation of an island structure in the subthreshold regime and the disappearance of the island structure at the ON state. These results were explained by the change in the effective number of CNTs that contributed to the electrical conduction due to the gate-bias-dependent resistance of the semiconducting CNTs. The results obtained by Monte Carlo simulation revealed similar results. The effects of metallic CNTs with defects and the scatter of the drain current in the subthreshold regime were also examined.

Sensing and actuating

195501

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Porphyrins may be used as photosensitizers for photodynamic therapy, photocatalysts for organic pollutant dissociation, agents for medical imaging and diagnostics, applications in luminescence and electronics. The detection of porphyrins is significantly important and here the interaction of protoporphyrin-IX (PPIX) with CdTe quantum dots was studied. It was observed that the luminescence of CdTe quantum dots was quenched dramatically in the presence of PPIX. When CdTe quantum dots were embedded into silica layers, almost no quenching by PPIX was observed. This indicates that PPIX may interact and alter CdTe quantum dots and thus quench their luminescence. The oxidation of the stabilizers such as thioglycolic acid (TGA) as well as the nanoparticles by the singlet oxygen generated from PPIX is most likely responsible for the luminescence quenching. The quenching of quantum dot luminescence by porphyrins may provide a new method for photosensitizer detection.

195502

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Herein, coordination polymer nanobelts (CPNBs) were prepared rapidly and on a large scale, by directly mixing aqueous AgNO3 solution and an ethanol solution of 4, 4'-bipyridine at room temperature. The application of such CPNBs as a fluorescent sensing platform for nucleic acid detection was further explored. CPNB is a π-rich structure, the strong π–π stacking interactions between unpaired DNA bases and CPNB leads to adsorption of fluorescently labeled single-stranded DNA (ssDNA) accompanied by 66% fluorescence quenching. However, the presence of target ssDNA will hybridize with the probe. The resultant helix cannot be adsorbed by CPNB due to its rigid conformation and the absence of unpaired DNA bases. Thus, a significant fluorescence enhancement, 73% fluorescence recovery, was observed in DNA detection as long as the target exists. The present system has excellent sensitivity; a substantial fluorescence enhancement was observed when the concentration of the target was as low as 5 nM. It also exhibits outstanding discrimination ability down to a single-base mismatch.

195503

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We used 40 ± 5 nm gold nanoparticles (GNPs) as colorimetric sensor to visually detect swine-specific conserved sequence and nucleotide mismatch in PCR-amplified and non-amplified mitochondrial DNA mixtures to authenticate species. Colloidal GNPs changed color from pinkish-red to gray-purple in 2 mM PBS. Visually observed results were clearly reflected by the dramatic reduction of surface plasmon resonance peak at 530 nm and the appearance of new features in the 620–800 nm regions in their absorption spectra. The particles were stabilized against salt-induced aggregation upon the adsorption of single-stranded DNA. The PCR products, without any additional processing, were hybridized with a 17-base probe prior to exposure to GNPs. At a critical annealing temperature (55 °C) that differentiated matched and mismatched base pairing, the probe was hybridized to pig PCR product and dehybridized from the deer product. The dehybridized probe stuck to GNPs to prevent them from salt-induced aggregation and retained their characteristic red color. Hybridization of a 27-nucleotide probe to swine mitochondrial DNA identified them in pork–venison, pork–shad and venison–shad binary admixtures, eliminating the need of PCR amplification. Thus the assay was applied to authenticate species both in PCR-amplified and non-amplified heterogeneous biological samples. The results were determined visually and validated by absorption spectroscopy. The entire assay (hybridization plus visual detection) was performed in less than 10 min. The LOD (for genomic DNA) of the assay was 6 µg ml − 1 swine DNA in mixed meat samples. We believe the assay can be applied for species assignment in food analysis, mismatch detection in genetic screening and homology studies between closely related species.

Materials: synthesis or self-assembly

195601

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Growth of GaAs and InxGa1 − xAs nanowires by the group-III assisted molecular beam epitaxy growth method on (001)GaAs/SiO2 substrates is studied in dependence on growth temperature, with the objective of maximizing the indium incorporation. Nanowire growth was achieved for growth temperatures as low as 550 °C. The incorporation of indium was studied by low temperature micro-photoluminescence spectroscopy, Raman spectroscopy and electron energy loss spectroscopy. The results show that the incorporation of indium achieved by lowering the growth temperature does not have the effect of increasing the indium concentration in the bulk of the nanowire, which is limited to 3–5%. For growth temperatures below 575 °C, indium rich regions form at the surface of the nanowires as a consequence of the radial growth. This results in the formation of quantum dots, which exhibit spectrally narrow luminescence.

195602

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The evolution of InAs and In0.85Mn0.15As quantum dots grown at 270 °C is studied as a function of coverage. We show that, in contrast to what occurs at high temperature, the two-dimensional to three-dimensional transition is not abrupt but rather slow. This is due to the finding that part of the deposited material also contributes to the wetting layer growth after quantum dot formation. This aspect is particularly accentuated in In0.85Mn0.15As deposition. The Voronoi area analysis reveals a significant spatial correlation between islands.

195603

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We demonstrate the use of thin BN sheets as supports for imaging nanocrystals using low voltage (80 kV) aberration-corrected high resolution transmission electron microscopy. This provides an alternative to the previously utilized 2D crystal supports of graphene and graphene oxide. A simple chemical exfoliation method is applied to get few layer boron nitride (BN) sheets with micrometer-sized dimensions. This generic approach of using BN sheets as supports is shown by depositing Mn doped ZnSe nanocrystals directly onto the BN sheets and resolving the atomic structure from both the ZnSe nanocrystals and the BN support. Phase contrast images reveal moiré patterns of interference between the beams diffracted by the nanocrystals and the BN substrate that are used to determine the relative orientation of the nanocrystals with respect to the BN sheets and interference lattice planes. Double diffraction is observed and has been analyzed.

195604

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Magnetically recyclable Ag–Ni core–shell nanoparticles have been fabricated via a simple one-pot synthetic route using oleylamine both as solvent and reducing agent and triphenylphosphine as a surfactant. As characterized by transmission electron microscopy (TEM), the as-synthesized Ag–Ni core–shell nanoparticles exhibit a very narrow size distribution with a typical size of 14.9 ± 1.2 nm and a tunable shell thickness. UV–vis absorption spectroscopy study shows that the formation of a Ni shell on Ag core can damp the surface plasmon resonance (SPR) of the Ag core and lead to a red-shifted SPR absorption peak. Magnetic measurement indicates that all the as-synthesized Ag–Ni core–shell nanoparticles are superparamagnetic at room temperature, and their blocking temperatures can be controlled by modulating the shell thickness. The as-synthesized Ag–Ni core–shell nanoparticles exhibit excellent catalytic properties for the generation of H2 from dehydrogenation of sodium borohydride in aqueous solutions. The hydrogen generation rate of Ag–Ni core–shell nanoparticles is found to be much higher than that of Ag and Ni nanoparticles of a similar size, and the calculated activation energy for hydrogen generation is lower than that of many bimetallic catalysts. The strategy employed here can also be extended to other noble-magnetic metal systems.

195605

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This work investigates the potential for harnessing the association of bacterial proteins to biogenic selenium nanoparticles (SeNPs) to control the size distribution and the morphology of the resultant SeNPs. We conducted a proteomic study and compared proteins associated with biogenic SeNPs produced by E. coli to chemically synthesized SeNPs as well as magnetite nanoparticles. We identified four proteins (AdhP, Idh, OmpC, AceA) that bound specifically to SeNPs and observed a narrower size distribution as well as more spherical morphology when the particles were synthesized chemically in the presence of proteins. A more detailed study of AdhP (alcohol dehydrogenase propanol-preferring) confirmed the strong affinity of this protein for the SeNP surface and revealed that this protein controlled the size distribution of the SeNPs and yielded a narrow size distribution with a three-fold decrease in the median size. These results support the assertion that protein may become an important tool in the industrial-scale synthesis of SeNPs of uniform size and properties.

195606

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TiO2 nanoparticles with controllable average diameter have been obtained by laser ablation in water. A monomode ytterbium doped fiber laser (YDFL) was used to ablate a metallic titanium target placed in deionized water. The resulting colloidal solutions were subjected to laser radiation to study the resizing effect. The crystalline phases, morphology and optical properties of the obtained nanoparticles were characterized by means of transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), x-ray energy dispersive spectroscopy (EDS) and UV–vis absorption spectroscopy. The colloidal suspensions produced consisting of titanium dioxide crystalline nanoparticles show almost perfect spherical shape with diameters ranging from 3 to 40 nm. The nanoparticles are polycrystalline and exhibit anatase as well as rutile phases.

195607

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CuInSe2 (CIS) nanodandelion structures were synthesized by a two-step solvothermal approach. First, InSe nanodandelions were prepared by reacting In(acac)3 with trioctylphosphine-selenide (TOP-Se) in 1-octadecene (ODE) at 170 °C in the presence of oleic acid. These InSe dandelions were composed of polycrystalline nanosheets with thickness < 10 nm. The size of the InSe dandelions could be tuned within the range of 300 nm–2 µm by adjusting the amount of oleic acid added during the synthesis. The InSe dandelion structures were then reacted with Cu(acac)2 in the second-step solvothermal process in ODE to form CIS nanodandelions. The band gap of the CIS dandelions was determined from ultraviolet (UV) absorption measurements to be ∼ 1.36 eV, and this value did not show any obvious change upon varying the size of the CIS dandelions. Brunauer–Emmett–Teller (BET) measurements showed that the specific surface area of these CIS dandelion structures was 44.80 m2 g − 1, which was more than five times higher than that of the CIS quantum dots (e.g.  8.22 m2 g − 1) prepared by using reported protocols. A fast photoresponsive behavior was demonstrated in a photoswitching device using the 200 nm CIS dandelions as the active materials, which suggested their possible application in optoelectronic devices.

Materials: properties, characterization or tools

195701

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We report on the layer-by-layer (LbL) formation of TiO2–MWNT–TiO2 coatings on quartz with either trititanate derived TiO2 nanowires or Degussa P25 as the photocatalytically active material. The optimized deposition sequence is discussed in detail and the morphology of the prepared coatings is analyzed by SEM and XRD. The heterogeneous photocatalytic performance of the coatings was tested in the methyl orange oxidation reaction. The apparent first order rate constant fell in the 0.01–0.20 h − 1 range over a 2.5 × 2.5 cm2 film depending on the type and the thickness of the titanate coating. Building a multiwall carbon nanotube layer into the middle of the layer improved the photocatalytic activity for each material for all of the studied thicknesses. P25 based films performed 2–5 times better than TiO2 nanowire films; however, the pores in the P25 based films were largely blocked because the isotropic P25 nanoparticles form closely packed layers by themselves and even more so with the comparably sized multiwall carbon nanotubes. Therefore, films derived from titanate nanowires appear to be more suitable for use as multifunctional, photocatalytically active filtration media.

195702

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The use of wavelet transforms in thermally excited dynamic force spectroscopy allows us to gain insight into the fundamental thermodynamical properties of a cantilever's Brownian motion as well as giving a meaningful and intuitive representation of the cantilever dynamics in time and frequency caused by the interaction with long- and short-range forces. The possibility of carrying out measurements across the jump-to-contact transition without interruption, providing information on both van der Waals forces and short-range adhesion surface forces, is remarkable.

195703

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A thin film of poly(3,4-ethylenedioxythiophene)–poly(4-styrenesulfonic acid) (PEDOT–PSS), which is an alternative cathodic catalyst for Pt in dye-sensitized solar cells, was prepared using the layer-by-layer self-assembly method (LbL). The film is highly adhesive to the substrate and has a controllable thickness. Therefore, the PEDOT–PSS film prepared using LbL is expected have high performance and durability as a counter electrode. Moreover, when carbon black was added to the PEDOT–PSS solution, highly mesoporous PEDOT–PSS and carbon black hybrid films were obtained. These films showed high cathodic activity. In this study, we investigated the change in morphology in the obtained film with increasing carbon black content, and the influence of the porosity and thickness on the performance of the cells. In this study, a Pt-free counter electrode with performance similar to that of Pt-based counter electrodes was successfully fabricated. The achieved efficiency of 4.71% was only a factor of 8% lower than that of the cell using conventional thermally deposited Pt on fluorine-doped tin oxide glass counter electrodes.

195704

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The excited state dynamics of core–shell type semiconductor quantum dots (QDs) of various sizes in close contact with a plasmonically active silver thin film has been demonstrated by using picosecond resolved fluorescence spectroscopy. The non-radiative energy transfer from the QDs to the metal surface is found to be of Förster resonance energy transfer (FRET) type rather than the widely expected nano-surface energy transfer (NSET) type. The slower rate of energy transfer processes compared to that of the electron transfer from the excited QDs to an organic molecule benzoquinone reveals an insignificant possibility of charge migration from the QDs to the metallic film.

195705

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The thermal decomposition of ultrathin HfO2 films (∼0.6–1.2 nm) on Si by ultrahigh vacuum annealing (25–800 °C) is investigated in situ in real time by scanning tunneling microscopy. Two distinct thickness-dependent decomposition behaviors are observed. When the HfO2 thickness is ∼ 0.6 nm, no discernible morphological changes are found below ∼ 700 °C. Then an abrupt reaction occurs at 750 °C with crystalline hafnium silicide nanostructures formed instantaneously. However, when the thickness is about 1.2 nm, the decomposition proceeds gradually with the creation and growth of two-dimensional voids at 800 °C. The observed thickness-dependent behavior is closely related to the SiO desorption, which is believed to be the rate-limiting step of the decomposition process.

195706

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Multifunctional single crystalline tin-doped indium oxide (ITO) nanowires with tuned Sn doping levels are synthesized via a vapor transport method. The Sn concentration in the nanowires can reach 6.4 at.% at a synthesis temperature of 840 °C, significantly exceeding the Sn solubility in ITO bulks grown at comparable temperatures, which we attribute to the unique feature of the vapor–liquid–solid growth. As a promising transparent conducting oxide nanomaterial, layers of these ITO nanowires exhibit a sheet resistance as low as and measurements on individual nanowires give a resistivity of 2.4 × 10 − 4 Ω cm with an electron density up to 2.6 × 1020 cm − 3, while the optical transmittance in the visible regime can reach ∼ 80%. Under the ultraviolet excitation the ITO nanowire samples emit blue light, which can be ascribed to transitions related to defect levels. Furthermore, a room temperature ultraviolet light emission is observed in these ITO nanowires for the first time, and the exciton-related radiative process is identified by using temperature-dependent photoluminescence measurements.

195707

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We study the high pressure response, up to 8 GPa, of silicon nanowires (SiNWs) with ∼ 15 nm diameter, by Raman spectroscopy. The first order Raman peak shows a superlinear trend, more pronounced compared to bulk Si. Combining transmission electron microscopy and Raman measurements we estimate the SiNWs' bulk modulus and the Grüneisen parameters. We detect an increase of Raman linewidth at ∼ 4 GPa, and assign it to pressure induced activation of a decay process into LO and TA phonons. This pressure is smaller compared to the ∼ 7 GPa reported for bulk Si. We do not observe evidence of phase transitions, such as discontinuities or change in the pressure slopes, in the investigated pressure range.