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Table of contents

Volume 25

Number 36, 12 September 2014

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Editorial

Topical review

362001
The following article is Open access

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The endeavor of exploiting arrays of vertical one-dimensional (1D) nanostructures (NSs) for cellular applications has recently been experiencing a pronounced surge of activity. The interest is rooted in the intrinsic properties of high-aspect-ratio NSs. With a height comparable to a mammalian cell, and a diameter 100–1000 times smaller, NSs should intuitively reach far into a cell and, due to their small diameter, do so without compromising cell health. Single NSs would thus be expedient for measuring and modifying cell response. Further organization of these structures into arrays can provide up-scaled and detailed spatiotemporal information on cell activity, an achievement that would entail a massive leap forward in disease understanding and drug discovery. Numerous proofs-of-principle published recently have expanded the large toolbox that is currently being established in this rapidly advancing field of research. Encouragingly, despite the diversity of NS platforms and experimental conditions used thus far, general trends and conclusions from combining cells with NSs are beginning to crystallize. This review covers the broad spectrum of NS materials and dimensions used; the observed cellular responses with specific focus on adhesion, morphology, viability, proliferation, and migration; compares the different approaches used in the field to provide NSs with the often crucial cytosolic access; covers the progress toward biological applications; and finally, envisions the future of this technology. By maintaining the impressive rate and quality of recent progress, it is conceivable that the use of vertical 1D NSs may soon be established as a superior choice over other current techniques, with all the further benefits that may entail.

Papers

Biology and medicine

365101

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Poly(amidoamine) (PAMAM) dendrimers are proposed as one of the most promising nanomaterials for biomedical applications because of their unique tree-like structure, monodispersity and tunable properties. In this study, we found that PAMAM dendrimers could induce the formation of autophagosomes and the conversion of microtubule-associated protein 1 light chain 3 (LC3) in hepatocellular carcinoma HepG2 cells, while the inhibition of the Akt/mTOR and activation of the Erk 1/2 signaling pathways were involved in autophagy-induced by PAMAM dendrimers. We also investigated the suppression of autophagy with the obviously enhanced cytotoxicity of PAMAM dendrimers. Moreover, the blockage of a reactive oxygen species (ROS) could enhance the growth inhibition and apoptosis of hepatocellular carcinoma cells, induced by PAMAM dendrimers through reducing autophagic effects. Taken together, these findings explored the role and mechanism of autophagy induced by PAMAM dendrimers in HepG2 cells, provided new insight into the effect of autophagy on drug delivery nanomaterials and tumor cells and contributed to the use of a drug delivery vehicle for hepatocellular carcinoma treatment.

Electronics and photonics

365201

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An electric-pulse-induced reversible resistance change effect in a molecular magnetic tunneling junction, consisting of a single-molecule magnet (SMM) sandwiched in one nonmagnetic and one ferromagnetic electrode, is theoretically investigated. By applying a time-varying bias voltage, the SMMʼs spin orientation can be manipulated with large bias voltage pulses. Moreover, the different magnetic configuration at high-resistance/low-resistance states can be 'read out' by utilizing relative low bias voltage. This device scheme can be implemented with current technologies (Khajetoorians et al 2013 Science339 55) and has potential application in molecular spintronics and high-density nonvolatile memory devices.

365202

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In this paper, we report on the fabrication and optoelectronic properties of high sensitive phototransistors based on few-layered MoSe2 back-gated field-effect transistors, with a mobility of 19.7 cm2 V−1 s−1 at room temperature. We obtained an ultrahigh photoresponsivity of 97.1 AW−1 and an external quantum efficiency (EQE) of 22 666% using 532 nm laser excitation at room temperature. The photoresponsivity was improved near the threshold gate voltage; however, the selection of the silicon dioxide as a gate oxide represents a limiting factor in the ultimate performance. Thanks to their high photoresponsivity and external quantum efficiency, the few-layered MoSe2-based devices are promising for photoelectronic applications.

365203

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Interface states influence the operation of nanocrystal (NC) solar cell carrier transport, recombination and energetic mechanisms. In a typical CdTe NC solar cell with a normal structure of a ITO/p-CdTe NCs/n-acceptor (or without)/Al configuration, the contact between the ITO and CdTe is a non-ohm contact due to a different work function (for an ITO, the value is ∼4.7 eV, while for CdTe NCs, the value is ∼5.3 eV), which results in an energetic barrier at the ITO/CdTe interface and decreases the performance of the NC solar cells. This work investigates how interface materials (including Au, MoOx and C60) affect the performance of NC solar cells. It is found that devices with interface materials have shown higher Voc than those without interface materials. For the case in which we used Au as an interface, we obtained a high open-circuit voltage of 0.65 V, coupled with a high fill factor (62%); this resulted in a higher energy conversion efficiency (ECE) of 5.3%, which showed a 30% increase in the ECE compared with those without the interlayer. The capacitance measurements indicate that the increased Voc in the case in which Au was used as the interface is likely due to good ohm contact between the Au's and the CdTe NCs' thin film, which decreases the energetic barrier at the ITO/CdTe interface.

Energy at the nanoscale

365401

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We report on thermoelectric transport measurements along the basal plane of several individual, single-crystalline Bi2Te3 nanowires (NWs) with different cross-sectional areas, grown by a vapor–liquid–solid method. Lithographically defined microdevices allowed us to determine the Seebeck coefficient S, electrical conductivity σ, and thermal conductivity κ of individual NWs. The NWs studied show near intrinsic transport properties with low electrical conductivities of around σ = (3.2 ± 0.9) × 104Ω−1 m−1 at room temperature. We observe a transition of the Seebeck coefficient from positive to negative values (S = +133 μVK−1 to S = −87 μVK−1) with increasing surface-to-volume ratio at room temperature, which can be explained by the presence of an approximately 5 nm thick Te-depleted layer at the surface of the NWs. The thermal conductivities of our NWs are in the range of κ = (1.4 ± 0.4) Wm−1 K−1 at room temperature, which is lower than literature values for bulk Bi2Te3. We attribute this suppression in thermal conductivity to enhanced scattering of phonons at the surface of the NWs. Despite their reduced thermal conductivities, the NWs investigated only show a moderate figure of merit between 0.02 and 0.18 due to their near intrinsic transport properties.

Sensing and actuating

365501

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This paper reports the numerical and experimental investigation of heat transfer from a heated microcantilever to a substrate and uses the resulting insights to improve thermal topography imaging. The cantilever sensitivity, defined as change in thermal signal due to changes in the topography height, is relatively constant for feature heights in the range 100–350 nm. Since the cantilever-substrate heat transfer is governed by thermal conduction through the air, the cantilever sensitivity is nearly constant across substrates of varying thermal conductivity. Surface features with lateral size larger than 2.5 μm can induce artifacts in the cantilever signal resulting in measurement errors as large as 28%. These artifacts arise from thermal conduction from the cantilever in the lateral direction, parallel to the surface. We show how these artifacts can be removed by accounting for this lateral conduction and removing it from the thermal signal. This technique reduces the measurement error by as much as 26%, can be applied to arbitrary substrate topographies, and can be scaled to arrays of heated cantilevers. These results could lead to improvements in nanometer-scale thermal measurements including scanning thermal microscopy and tip-based nanofabrication.

365502

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High sensitivity zinc oxide (ZnO) tetrapods (TPs) have been functionalized by nucleating cadmium sulphide (CdS) nanoparticles (NPs) directly on their surface with a spotted coverage thanks to an optimized synthesis in dimethylformamide (DMF). The obtained hybrid coupled material has been used to realize a gas sensing device with a highly porous nanostructured network, in which the proper alternation of ZnO-TPs and CdS-NPs gives rise to unconventional chemoresistive behaviours. Among the different tested gases and vapours, the sensor showed a unique fingerprint response-inversion between 300 °C and 400 °C only for nitrogen dioxide (NO2) and acetic acid (CH3COOH).

Materials: synthesis or self-assembly

365601

We predict the stability of diamondoids made up of boron and nitrogen instead of carbon atoms. The results are based on quantum-mechanical calculations within density functional theory (DFT) and show some very distinct features compared to the regular carbon-based diamondoids. These features are evaluated with respect to the energetics and electronic properties of the boron nitride diamondoids as compared to the respective properties of the carbon-based diamondoids. We find that BN-diamondoids are overall more stable than their respective C-diamondoid counterparts. The electronic band-gaps (Eg) of the former are overall lower than those for the latter nanostructures but do not show a very distinct trend with their size. Contrary to the lower C-diamondoids, the BN-diamondoids are semiconducting and show a depletion of charge on the nitrogen site. Their differences in the distribution of the molecular orbitals, compared to their carbon-based counterparts, offer additional bonding and functionalization possibilities. These tiny BN-based nanostructures could potentially be used as nanobuilding blocks complementing or substituting the C-diamondoids, based on the desired properties. An experimental realization of boron nitride diamondoids remains to show their feasibility.

365602

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In this study, we present a facile one-step method to synthesize graphene-Au nanoparticle (NP) hybrid materials by using HAuCl4-loaded poly(styrene)-block-poly(2-vinylpyridine) (PS-P2VP) micelles as solid carbon sources. N-doped graphene with controllable thickness can be grown from PS-P2VP micelles covered by a Ni capping layer by an annealing process; simultaneously, the HAuCl4 in the micelles were reduced into Au NPs under a reductive atmosphere to form Au NPs on graphene. The decoration of Au NPs leads to an obviously enhanced electrical conductivity and a slightly increased work function of graphene due to the electron transfer effect. The graphene-Au NP hybrid materials also exhibit a localized surface plasmon resonance feature of Au NPs. This work provides a novel and accessible route for the one-step synthesis of graphene-Au NP hybrid materials with high quality, which might be useful for future applications in optoelectronic devices.

365603

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The chemical vapor deposition of monolayer and few-layer transition metal dichalcogenides is a rapidly developing area of materials science due to the exciting electrical, optical, thermal and mechanical properties of transition metal dichalcogenides in their layered form. These properties make these innovative materials potentially relevant to wide-ranging commercial applications. One of these promising materials is MoSe2; however, just recently, a few research groups have been able to demonstrate its synthesis via chemical vapor deposition. Moreover, only oriented few-layer MoSe2 has been exhibited by synthetically formed material using chemical vapor deposition thus far. Here, we confirm twisted-layer MoSe2 can also form during chemical vapor deposition. Twisted-layer transition metal dichalcogenides alter their properties as compared to their oriented counterparts. Therefore, twisted-layer structures are of interest because they can tune their properties.

Materials: properties, characterization or tools

365701

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Metallic implants and devices are widely used in the orthopedic and orthodontic clinical areas. However, several problems regarding their adhesion with the living tissues and inflammatory responses due to the release of metallic ions to the medium have been reported. The modification of the metallic surfaces and the use of biocompatible protective coatings are two approaches to solve such issues. In this study, in order to improve the adhesion properties and to increase the corrosion resistance of metallic Ti substrates we have obtained a hybrid structure based on TiO2 nanotubular arrays and PDMS-TEOS films. TiO2 nanotubes have been prepared with two different diameters by means of electrochemical anodization. PDMS-TEOS films have been prepared by the sol–gel method. The morphological and the elemental analysis of the structures have been investigated by scanning electron microscopy and energy dispersive spectroscopy (EDS). Electrochemical impedance spectroscopy (EIS) and polarization curves have been performed during immersion of the samples in Kokubo's simulated body fluid (SBF) at 37 °C to study the effect of structure layers and tube diameter on the protective properties. The obtained results show that the modification of the surface structure of TiO2 and the application of PDMS-TEOS film is a promising strategy for the development of implant materials.