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Table of contents

Volume 24

Number 34, 30 August 2013

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Perspective

342501

The sequencing of the human genome offered a glimpse of future medical practices, where information retrieved from the genome could be harnessed to inform treatment decisions. However, making DNA sequencing accessible enough for widespread use poses a number of challenges. This perspective article traces the progress made in the field so far and looks at how close we may be already to real-life applications.

Papers

Biology and medicine

345101

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We report on the dose-dependent inhibition of firefly luciferase activity induced by exposure of the enzyme to 20 nm citrate-coated silver nanoparticles (AgNPs). The inhibition mechanism was examined by characterizing the physicochemical properties and biophysical interactions of the enzyme and the AgNPs. Consistently, binding of the enzyme induced an increase in zeta potential from −22 to 6 mV for the AgNPs, triggered a red-shift of 44 nm in the absorbance peak of the AgNPs, and rendered a 'protein corona' of 20 nm in thickness on the nanoparticle surfaces. However, the secondary structures of the enzyme were only marginally affected upon formation of the protein corona, as verified by circular dichroism spectroscopy measurement and multiscale discrete molecular dynamics simulations. Rather, inductively coupled plasma mass spectrometry measurement revealed a significant ion release from the AgNPs. The released silver ions could readily react with the cysteine residues and N-groups of the enzyme to alter the physicochemical environment of their neighboring catalytic site and subsequently impair the enzymatic activity.

Electronics and photonics

345201

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High crystal quality, vertically aligned AlxGa1−xN nanowire based double heterojunction light emitting diodes (LEDs) are grown on Si substrate by molecular beam epitaxy. Such AlxGa1−xN nanowires exhibit unique core–shell structures, which can significantly suppress surface nonradiative recombination. We successfully demonstrate highly efficient AlxGa1−xN nanowire array based LEDs operating at ∼340 nm. Such nanowire devices exhibit superior electrical and optical performance, including an internal quantum efficiency of ∼59% at room temperature, a relatively small series resistance, highly stable emission characteristics, and the absence of efficiency droop under pulsed biasing conditions.

345202

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The growing demand for biomaterials for electrical and optical devices is motivated by the need to make building blocks for the next generation of printable bio-electronic devices. In this study, transparent and flexible resistive memory devices with a very high ON/OFF ratio incorporating gold nanoparticles into the Bombyx mori silk protein fibroin biopolymer are demonstrated. The novel electronic memory effect is based on filamentary switching, which leads to the occurrence of bistable states with an ON/OFF ratio larger than six orders of magnitude. The mechanism of this process is attributed to the formation of conductive filaments through silk fibroin and gold nanoparticles in the nanocomposite. The proposed hybrid bio-inorganic devices show promise for use in future flexible and transparent nanoelectronic systems.

345203

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Unlike common metals, graphene can support transverse electric (TE) surface modes when the imaginary part of its conductivity is negative. We have theoretically investigated and numerically simulated plasmonic properties of graphene TE surface plasmons (SPs) in the terahertz regime. The influence of the external magnetic field, gate voltage and temperature as the tuning schemes of the SPs have been investigated. The results show that graphene TE modes can be realized by tuning the magnetic fields or gate voltage. If the permeability of the dielectrics on both sides of the graphene layer differs enough, the graphene TE modes can still be achieved. The work presented here has the potential for application to graphene-based plasmonic devices in photonics and optoelectronics, such as sensors, polarizers and modulators.

Patterning and nanofabrication

345301

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The current understanding in the study of focused electron beam induced processing (FEBIP) is that the growth of a deposit is mainly the result of secondary electrons (SEs). This suggests that the growth rate for FEBIP is affected by the SE emission from the support. Our experiments, with membranes thinner than the SE escape depth, confirm this hypothesis. We used membranes of 1.4 and 4.3 nm amorphous carbon as supports. At the very early stage, the growth is support-dominated and the growth rate on a 4.3 nm thick membrane is three times higher than on a 1.4 nm thick membrane. This is consistent with Monte Carlo simulations for SE emission. The results suggest that SEs are dominant in the dissociation of W(CO)6 on thin membranes. The best agreement between simulations and experiment is obtained for SEs with energies between 3 and 6 eV.

With this work we revisit earlier experiments, working at a precursor pressure 20 times lower than previously. Then, despite using membranes thinner than the SE escape depth, we did not see an effect on the experimental growth rate. We explain our current results by the fact that very early in the process, the growth becomes dominated by the growing deposit itself.

Energy at the nanoscale

345401

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The great advances in nanotechnology call for advances in miniaturized power sources for micro/nano-scale systems. Nanofluidic channels have received great attention as promising high-power-density substitutes for ion exchange membranes for use in energy harvesting from ambient ionic concentration gradient, namely reverse electrodialysis. This paper proposes the nanofluidic crystal (NFC), of packed nanoparticles in micro-meter-sized confined space, as a facile, high-efficiency and high-power-density scaling-up scheme for energy harvesting by nanofluidic reverse electrodialysis (NRED). Obtained from the self-assembly of nanoparticles in a micropore, the NFC forms an ion-selective network with enormous nanochannels due to electrical double-layer overlap in the nanoparticle interstices. As a proof-of-concept demonstration, a maximum efficiency of 42.3 ± 1.84%, a maximum power density of 2.82 ± 0.22 W m−2, and a maximum output power of 1.17 ± 0.09 nW/unit (nearly three orders of magnitude of amplification compared to other NREDs) were achieved in our prototype cell, which was prepared within 30 min. The current NFC-based prototype cell can be parallelized and cascaded to achieve the desired output power and open circuit voltage. This NFC-based scaling-up scheme for energy harvesting based on NRED is promising for the building of self-powered micro/nano-scale systems.

345402

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A colloidal deposition technique is presented to construct long-range ordered hybrid arrays of self-assembled quantum dots and metal nanoparticles. Quantum dots are promising for novel opto-electronic devices but, in most cases, their optical transitions of interest lack sufficient light absorption to provide a significant impact in their implementation. A potential solution is to couple the dots with localized plasmons in metal nanoparticles. The extreme confinement of light in the near-field produced by the nanoparticles can potentially boost the absorption in the quantum dots by up to two orders of magnitude.

In this work, light extinction measurements are employed to probe the plasmon resonance of spherical gold nanoparticles in lead sulfide colloidal quantum dots and amorphous silicon thin-films. Mie theory computations are used to analyze the experimental results and determine the absorption enhancement that can be generated by the highly intense near-field produced in the vicinity of the gold nanoparticles at their surface plasmon resonance.

The results presented here are of interest for the development of plasmon-enhanced colloidal nanostructured photovoltaic materials, such as colloidal quantum dot intermediate-band solar cells.

Sensing and actuating

345501

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Plasmonic substrates were prepared by electrophoretic deposition of Ag nanoparticles on SiO2/Si(100). The Ag nanoparticles were obtained using [Ag(NH3)2]+ as the Ag precursor and d-glucose as the reducing agent. Under optimized conditions, this simple and green synthesis method furnished a suspension of Ag nanoparticles with a narrow dimensional dispersion (centered around 27 nm) and a negative z-potential, suitable for electrophoretic deposition. Samples were chemically, optically and morphologically characterized by photoemission and UV–vis spectroscopy and electron microscopy, and tested as substrates for surface enhanced Raman spectroscopy. Despite being a very simple procedure, good enhancement factors were measured thanks to the formation of hot spots, formed by sandwiching the analyte (benzenethiol) between sequentially deposited Ag nanoparticles.

345502

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Double-stranded DNAs (ds-DNAs) have been identified as efficient templates favoring the formation of fluorescent copper nanoparticles (Cu NPs). Herein, we have tried to synthesize fluorescent Cu NPs using single-stranded DNAs (ss-DNAs) as templates and to identify the critical DNA sequences. By comparing the results using homopolymer DNAs, hairpin DNAs, and pristine ss-DNAs as templates, we found that DNA thymine base plays a dominant role in producing red-emissive fluorescent Cu NPs on ss-DNA templates. The thymine-dependent growth of the fluorescent Cu NPs is confirmed by Hg2+ mediated T–T base pair in comparison with the other non-specific metal ions, which could be developed into a practical sensor for turn-on fluorescence detection of Hg2+ with a high selectivity. The mechanism is briefly discussed according the DNA sequence-dependent formation of fluorescent Cu NPs. This work demonstrates the sequence role in producing fluorescent Cu NPs that could serve as promising fluorescent nanoprobes in biosensing and DNA-hosted Cu nanomaterials.

Materials: synthesis or self-assembly

345601

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Nanowire heterostructures are of special interest for band structure engineering due to an expanded range of defect-free material combinations. However, the higher degree of freedom in nanowire heterostructure growth comes at the expense of challenges related to nanowire–seed particle interactions, such as undesired composition, grading and kink formation. To better understand the mechanisms of kink formation in nanowires, we here present a detailed study of the dependence of heterostructure nanowire morphology on indium pressure, nanowire diameter, and nanowire density. We investigate InAs–InP–InAs heterostructure nanowires grown with chemical beam epitaxy, which is a material system that allows for very abrupt heterointerfaces. Our observations indicate that the critical parameter for kink formation is the availability of indium, and that the resulting morphology is also highly dependent on the length of the InP segment. It is shown that kinking is associated with the formation of an inclined facet at the interface between InP and InAs, which destabilizes the growth and leads to a change in growth direction. By careful tuning of the growth parameters, it is possible to entirely suppress the formation of this inclined facet and thereby kinking at the heterointerface. Our results also indicate the possibility of producing controllably kinked nanowires with a high yield.

345602

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In this work, SnO2 quantum dots with high crystallinity were synthesized on a large scale under mild reaction conditions via an epoxide precipitation route. The SnO intermediate, which was produced in the reactions between epoxide and [Sn(H2O)6]2+, was converted to SnO2 quantum dots by the oxidation of H2O2. It is believed that the protonation and the following ring opening of epoxide promoted the hydrolysis and condensation of [Sn(H2O)6]2+ to form the intermediate. The obtained quantum dots had a maximum specific capacitance of 204.4 F g−1 at a scan rate of 5 mV s−1 in 1 mol l−1 KOH aqueous solution. The electrochemical measurements proved that this high specific capacitance of SnO2 resulted from the Faradaic reactions between SnO2 and the electrolyte. This demonstrates for the first time that SnO2 can be used as a pseudocapacitive electrode material.

345603

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Multifunctional mesoporous silica nanocomposites are attractive carriers for targeted drug delivery in nanomedicine. Although promising developments have been made in the fabrication of multifunctional mesoporous silica nanocomposites, the design and mass production of novel multifunctional carriers are still challenging. This paper reports the facile one-pot fabrication of a multifunctional inorganic composite composed of superparamagnetic Fe3O4 nanoparticles and coated dye-functionalized mesoporous silica with a high specific surface area. The resulting composite particles had a tunable particle size, special open pore channels with high specific surface area, which is quite favorable for drug loading and release properties, as well as luminescent and superparamagnetic properties suitable for targeted drug delivery and tracking. This composite exhibited low toxicity, suggesting potential biomedical applications.

345604

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Control of the shape and size of nanoparticles is crucial for using them as labels or as building blocks in nanotechnology. In fact, silver has so far been considered as having the widest variety of different morphologies at the nano-scale and micro-scale levels. To make progress in these criteria, in our paper we have synthesized highly reproducible silver (Ag) microrods of controlled aspect ratios through a rapid self-seeding method. The Ag nano seeds are formed via the reduction of Ag ions in hot ethylene glycol by ascorbic acid, and the subsequent growth of microrods is controlled by further deposition of Ag atoms in the presence of poly(vinylpyrrolidone). Moreover, ascorbic acid is exclusively responsible for the rod morphology, as we describe here in detail. A very low concentration of ascorbic acid forms very few Ag microrods along with a majority of Ag colloidal particles, while random overgrowth on the surfaces is observed for higher concentrations. The critical reaction condition has been found in that the aspect ratio of the Ag microrods can be systematically tuned between 4 and 90. Also, the method in which ascorbic acid is added to the reaction medium plays a key role in controlling the aspect ratio of the Ag microrods. The non-monotonic dependence of the length and the diameter of the Ag microrods has been described by an empirical equation. The function can be interpreted by means of concentration-dependent competition between the adsorption of ligands and metal deposition.

345605

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We report here a novel synthetic method to prepare monodisperse air-stable FeCo nanoparticles with average sizes of 8, 12 and 20 nm. CoFe2O4 nanoparticles of different sizes were first synthesized by a chemical solution method. The as-synthesized CoFe2O4 nanoparticles were then mixed with ball-milled NaCl powders and heated to 400–500 ° C in forming gas (Ar 93%+H2 7%). The salt powder worked as a separating medium that prevents the CoFe2O4 nanoparticles from agglomerating during the heat treatment while the forming gas reduces the CoFe2O4 nanoparticles to FeCo nanoparticles. Monodisperse FeCo nanoparticles were recovered by dissolving the NaCl in water and subsequently washing with ethanol and acetone. Structural analyses confirmed that FeCo nanoparticles retained the same size as their oxide precursors. The size of the FeCo nanoparticles can be well tuned by controlling the size of the CoFe2O4 nanoparticles. The saturation magnetization of FeCo nanoparticles is size dependent and increases with size.

Materials: properties, characterization or tools

345701

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Using Raman spectroscopy, we demonstrated photothermally induced crystallographic phase transitions of vanadium dioxide (VO2) nanobeams clamped to and free-standing on a substrate. Compared to the temperature-dependent Raman measurements, the laser-power-dependent Raman characteristics provide substantial evidence for the photothermal origin of the phase transitions of the VO2 nanobeams. The laser power necessary to cause phase transitions in the free-standing nanobeam was approximately eight times smaller than the laser power used in the substrate-clamped nanobeam. Our study will enhance the understanding of the complex phase transitions of strongly correlated oxides and thereby provide a foundation for engineering desirable properties in novel devices.

345702

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The alignment of liquid crystals (LCs) on zinc oxide (ZnO) nanorods grown vertically on an indium tin oxide (ITO) layer has been investigated as an alternative alignment layer for the vertical alignment of LCs. We found that the degree of vertical alignment strongly depends on the length and density of the vertically aligned ZnO nanorods on the ITO layer and also that a uniform vertical alignment using the proposed structure can be achieved. Finally, vertically aligned LC cells with ZnO nanorods were fabricated and their electro-optical properties were evaluated and compared with those of a conventional vertically aligned LC cell with a polymer alignment layer.

345703

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Applications based on the movement of domain walls (DWs) in magnetic nanowires (NWs) require a good DW conduit behavior, i.e. a significant difference between DW nucleation and propagation fields. In this work, we have systematically studied how this property evolves in cobalt NWs grown by focused electron beam induced deposition (FEBID) as a function of global gallium irradiation, for irradiation doses up to 1.24 × 1017 ions cm−2. Whereas for high doses the DW conduit is lost, below 6.42 × 1015 ions cm−2 the difference between the two fields increases with irradiation, becoming up to ∼9 times larger than for non-irradiated wires, due to a strong increase in the nucleation field, while the propagation field remains approximately constant. This behavior stems from two effects. The first effect is a decrease in the magnetic volume of the parasitic halo around the NW, typically present in FEBID nanostructures, leading to the disappearance of weak nucleation centers. The second effect is the formation of a 20 nm outer shell with Co crystals about twice the size of those forming the NW core, causing a net increase of the local magnetocrystalline anisotropy. The results presented here are important for the potential use of magnetic NWs grown by FEBID in DW-based devices, and might also be of interest for magnetic NWs fabricated by other techniques.

345704

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Delafossite CuCrO2 and spinel CuCr2O4 with mesoporous structures have been successfully synthesized using nanocasting methods based on a KIT-6 template. The functional activity of the mesoporous materials was evaluated in applications as heterogeneous catalysts. The activity for photocatalytic hydrogen production of the delafossite structures with different morphologies was characterized and the oxidation state changes associated with photocorrosion of Cu+ investigated using electron energy loss spectroscopy (EELS). Mg2+ doping was found to facilitate the casting of ordered structures for CuCrO2 and improves the photocorrosion resistance of delafossite structures. The mesoporous spinel CuCr2O4 nanostructures were found to be active for low temperature CO oxidation.

345705

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In the present work, the effect of aluminum (Al) on the thermoelectric properties of PbTe is studied. Aluminum doped PbTe samples, fabricated by a ball milling and hot pressing, have Seebeck coefficients between −100 and −200 μV K−1 and electrical conductivities of (3.6–18) × 104 S m−1 at room temperature, which means that Al is an effective donor in PbTe. The first principle calculations clearly show an increase of the density of states close to the Fermi level in the conduction band due to Al doping, which averages up the energy and effective mass of electrons, resulting in enhancement of the Seebeck coefficient. The maximum figure-of-merit ZT of 1.2 is reached at 770 K in the Al0.03PbTe sample.