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Table of contents

Volume 27

Number 41, 14 October 2016

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Letter

41LT01

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Sorted single-walled carbon nanotubes (SWNTs) are of paramount importance for their utilization in high-end optoelectronic applications. Sodium cholate (SC)-based density gradient ultracentrifugation (DGU) has been instrumental in isolating small diameter (dt) SWNTs. Here, we show that SWNTs wrapped by flavin mononucleotide (FMN) as a dispersing agent are sorted in DGU, and show sorting order reversal behavior, departing from prototypical SC-SWNT trends. Larger dt SWNTs are sorted in lower density (ρ), and buoyant ρ distribution of FMN-SWNT ranges from 1.15–1.25 g cm−3. Such a nanotube layering pattern originates from both the binding affinity between FMN and SWNT and the less-susceptible hydrated volume of remote phosphate sidechains of FMN according to nanotube dt change.

Topical Review

412001

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Nanoscale metamaterials

Optical chiral metamaterials have recently attracted considerable attention because they offer new and exciting opportunities for fundamental research and practical applications. Through pragmatic designs, the chiroptical response of chiral metamaterials can be several orders of magnitude higher than that of natural chiral materials. Meanwhile, the local chiral fields can be enhanced by plasmonic resonances to drive a wide range of physical and chemical processes in both linear and nonlinear regimes. In this review, we will discuss the fundamental principles of chiral metamaterials, various optical chiral metamaterials realized by different nanofabrication approaches, and the applications and future prospects of this emerging field.

412002

and

The unique features of nanomaterials have led to their rapid development in the biomedical field. In particular, functionalized nanoparticles (NPs) are extensively used in the delivery of drugs and genes, bio-imaging and diagnosis. Hence, the interaction between NPs and cells is one of the most important issues towards understanding the true nature of the NP-mediated biological effects. Moreover, the intracellular safety concern of the NPs as a result of intracellular NP degradation remains to be clarified in detail. This review presents recent advances in the interactions of designed NPs and cells. The focus includes the governing factors on cellular uptake and the intracellular fate of NPs, and the degradation of NPs and its influence on nanotoxicity. Some basic consideration is proposed for optimizing the NP-cell interaction and designing NPs of better biocompatiblity for biomedical application.

412003

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There are a range of different methods to generate a nanostructured surface on silicon (Si) but the most cost effective and optically interesting is the metal assisted wet chemical etching (MACE) (Koynov et al 2006 Appl. Phys. Lett.88 203107). MACE of Si is a controllable, room-temperature wet-chemical technique that uses a thin layer of metal to etch the surface of Si, leaving behind various nano- and micro-scale surface features or 'black silicon'. MACE-fabricated nanowires (NWs) provide improved antireflection and light trapping functionality (Toor et al 2016 Nanoscale8 15448–66) compared with the traditional 'iso-texturing' (Campbell and Green 1987 J. Appl. Phys.62243–9). The resulting lower reflection and improved light trapping can lead to higher short circuit currents in NW solar cells (Toor et al 2011 Appl. Phys. Lett.99 103501). In addition, NW cells can have higher fill factors and voltages than traditionally processed cells, thus leading to increased solar cell efficiencies (Cabrera et al 2013 IEEE J. Photovolt.3102–7). MACE NW processing also has synergy with next generation Si solar cell designs, such as thin epitaxial-Si and passivated emitter rear contact (Toor et al 2016 Nanoscale8 15448–66). While several companies have begun manufacturing black Si, and many more are researching these techniques, much of the work has not been published in traditional journals and is publicly available only through conference proceedings and patent publications, which makes learning the field challenging. There have been three specialized review articles published recently on certain aspects of MACE or black Si, but do not present a full review that would benefit the industry (Liu et al 2014 Energy Environ. Sci.73223–63; Yusufoglu et al 2015 IEEE J. Photovolt.5320–8; Huang et al 2011 Adv. Mater.23 285–308). In this feature article, we review the chemistry of MACE and explore how changing parameters in the wet etch process effects the resulting texture on the Si surface. Then we review efforts to increase the uniformity and reproducibility of the MACE process, which is critical for commercializing the black Si technology.

Focus Issue Papers

414001

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3d printing

Osteochondral tissue has a complex graded structure where biological, physiological, and mechanical properties vary significantly over the full thickness spanning from the subchondral bone region beneath the joint surface to the hyaline cartilage region at the joint surface. This presents a significant challenge for tissue-engineered structures addressing osteochondral defects. Fused deposition modeling (FDM) 3D bioprinters present a unique solution to this problem. The objective of this study is to use FDM-based 3D bioprinting and nanocrystalline hydroxyapatite for improved bone marrow human mesenchymal stem cell (hMSC) adhesion, growth, and osteochondral differentiation. FDM printing parameters can be tuned through computer aided design and computer numerical control software to manipulate scaffold geometries in ways that are beneficial to mechanical performance without hindering cellular behavior. Additionally, the ability to fine-tune 3D printed scaffolds increases further through our investment casting procedure which facilitates the inclusion of nanoparticles with biochemical factors to further elicit desired hMSC differentiation. For this study, FDM was used to print investment-casting molds innovatively designed with varied pore distribution over the full thickness of the scaffold. The mechanical and biological impacts of the varied pore distributions were compared and evaluated to determine the benefits of this physical manipulation. The results indicate that both mechanical properties and cell performance improve in the graded pore structures when compared to homogeneously distributed porous and non-porous structures. Differentiation results indicated successful osteogenic and chondrogenic manipulation in engineered scaffolds.

414002

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Biosensing

Small diamond-like particles, diamondoids, have been shown to effectively functionalize gold electrodes in order to sense DNA units passing between the nanopore-embedded electrodes. In this work, we present a comparative study of Au(111) electrodes functionalized with different derivatives of lower diamondoids. Focus is put on the electronic and transport properties of such electrodes for different DNA nucleotides placed within the electrode gap. The functionalization promotes a specific binding to DNA leading to different properties for the system, which provides a tool set to systematically improve the signal-to-noise ratio of the electronic measurements across the electrodes. Using quantum transport calculations, we compare the effectiveness of the different functionalized electrodes in distinguishing the four DNA nucleotides. Our results point to the most effective diamondoid functionalization of gold electrodes in view of biosensing applications.

414003

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Focus on Scanning Probe Microscopy

We develop and implement a multifrequency spectroscopy and spectroscopic imaging mode, referred to as general dynamic mode (GDM), that captures the complete spatially- and stimulus dependent information on nonlinear cantilever dynamics in scanning probe microscopy (SPM). GDM acquires the cantilever response including harmonics and mode mixing products across the entire broadband cantilever spectrum as a function of excitation frequency. GDM spectra substitute the classical measurements in SPM, e.g. amplitude and phase in lock-in detection. Here, GDM is used to investigate the response of a purely capacitively driven cantilever. We use information theory techniques to mine the data and verify the findings with governing equations and classical lock-in based approaches. We explore the dependence of the cantilever dynamics on the tip–sample distance, AC and DC driving bias. This approach can be applied to investigate the dynamic behavior of other systems within and beyond dynamic SPM. GDM is expected to be useful for separating the contribution of different physical phenomena in the cantilever response and understanding the role of cantilever dynamics in dynamic AFM techniques.

414004

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Focus on Scanning Probe Microscopy

Fourier-transform scanning tunnelling spectroscopy (FT-STS), or quasiparticle interference, has become an influential tool for the study of a wide range of important materials in condensed matter physics. However, FT-STS in complex materials is often challenging to interpret, requiring significant theoretical input in many cases, making it crucial to understand potential artifacts of the measurement. Here, we compare the most common modes of acquiring FT-STS data and show through both experiment and simulations that artifact features can arise that depend on how the tip height is stabilized throughout the course of the measurement. The most dramatic effect occurs when a series of dI/dV maps at different energies are acquired with simultaneous constant current feedback; here a feature that disperses in energy appears that is not observed in other measurement modes. Such artifact features are similar to those arising from real physical processes in the sample and are susceptible to misinterpretation.

414005

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Focus on 2D materials beyond graphene

Due to the matching surface energy, WS2 quantum dots (QDs) can be obtained through direct liquid exfoliation in N-methyl-2-pyrrolidone rather than an ethanol and water mixture. Ultra-small WS2 QDs with a diameter of 2.4 nm are fabricated by an ultrasound method followed by high speed centrifugation up to 10 000 rpm. An excellent nonlinear optical (NLO) property of the WS2 QD/ polymethylmethacrylate (PMMA) composite for the nanosecond pulsed laser at both 532 and 1064 nm has been measured. Results illustrate the lower onset thresholds (FON), lower optical limiting thresholds (FOL), and higher two-photon absorption coefficient (β) with respect to a higher concentration of embedded WS2 QDs into the PMMA solid state matrix for both 532 and 1064 nm.

414006

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Focus on 2D materials beyond graphene

We report a simple method to prepare a thin Tungsten Telluride (WTe2) flake with accurate thickness control, which allows preparing and studying this two dimensional material conveniently. First, the WTe2 flake, which is relatively thick due to its strong interlayer van der Waals forces, is obtained by a conventional mechanical exfoliation method. Then, the exfoliated flake is annealed at 600 °C under a constant Ar protecting flow. Raman and atomic force spectroscopy characterizations demonstrate that thermal annealing can effectively thin down the WTe2 flake and retain its original lattice structure, though its surface smoothness is slightly deteriorated. Additionally, systematical study indicates that the thinning process strongly depends on the initial thickness of the WTe2 flake before annealing: the thinning rate increases from 0.12 nm min−1 to 0.36 nm min−1 as the initial thickness increases from 10 nm to 45 nm, while the roughness of the final product also increases with the increase of its initial thickness. However, the method fails when it is applied to WTe2 flakes thicker than 100 nm, resulting in uneven or burnt surface, which is possibly caused by big cavities formed by a large amount of defects gathered at the top surface.

Papers

Electronics and photonics

415201

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In this article we demonstrate type-II band alignment at the wurtzite/zinc-blende hetero-interface in InAs polytype nanowires using resonance Raman measurements. Nanowires were grown with an optimum ratio of the above mentioned phases, so that in the electronic band alignment of such NWs the effect of the difference in the crystal structure dominates over other perturbing effects (e.g. interfacial strain, confinement of charge carriers and band bending due to space charge). Experimental results are compared with the band alignment obtained from density functional theory calculations. In resonance Raman measurements, the excitation energies in the visible range probe the band alignment formed by the E1 gap of wurtzite and zinc-blende phases. However, we expect our claim to be valid also for band alignment near the fundamental gap at the heterointerface.

415202

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Graphene (G), TiO2 fusiform nanorods (TiO2NRs) adsorbed with Au nanoparticles (AuNPs) are prepared and blended as multifunctional materials into TiO2 nanocrystalline film to form a novel ternary (G-TiO2NRs-Au) composite photoanode in dye-sensitized solar cells (DSSCs). The effects of G-TiO2NRs-Au on the properties of the photoanode and DSSC are investigated. Results show that, by blending G-TiO2NRs-Au, the light absorption and scattering of the photoanode are obviously improved, and the charge transfer resistance R2 and electron recombination are decreased, resulting in a significant enhancement in the short-circuit current density (Jsc) and the photoelectric conversion efficiency (PCE) of the DSSCs. The maximum Jsc of 17.66 mA cm−2 and PCE of 8.56% are obtained in the optimal G-TiO2NRs-Au-based DSSC, about 33.6% and 35.0% higher than that obtained in the conventional TiO2-based DSSC. This significant improvement in the performance of the DSSC can be attributed to the ternary composite complementary effects of multi-functions from the surface plasmon resonance of AuNPs, light scattering of TiO2NRs, and the improved dye loading and fast electron transmission channel from graphene. This study provides an effective way of ternary composite complementary enhancement of the Jsc and PCE of the DSSCs.

415203

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Because of the excellent physical and chemical properties of phosphorene, phosphorene and phosphorene-like materials have attracted extensive attention. Since phosphorus belongs to group V, some group IV-VI compounds could also form phosphorene-like configurations. In this work, GeO, SnO, GeS, and SnS monolayers were constructed to investigate the structural and electronic properties by employing first-principles computations. Phonon spectra suggest that these monolayers are dynamically stable and could be realized in experiments. These monolayers are all semiconductors with the band gaps of 2.26 ∼ 4.13 eV. Based on the monolayers, GeO, SnO, GeS, and SnS bilayers were also constructed. The band gaps of these bilayers are smaller than those of the corresponding monolayers. Moreover, the optical properties of these monolayers and bilayers were calculated, and the results indicate that the SnO, GeS and SnS bilayers exhibit obvious optical absorption in the visible spectrum. All the results suggest that phosphorene-like IV-VI materials are promising candidates for electronic and optical devices.

415204

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We report experimental observation of intrinsic Bloch-mode emission from a 3D tungsten photonic crystal at low thermal excitation. After the successful removal of conventional metallic emission (normal emission), it is possible to make an accurate comparison of the Bloch-mode and the normal emission. For all biases, we found that the emission intensity of the Bloch-mode is higher than that of the normal emission. The Bloch-mode emission also exhibits a slower dependence on $(\hslash \omega /{k}_{b}T)$ than that of the normal emission. The observed higher emission intensity and a different T-dependence is attributed to Bloch-mode assisted emission where emitters have been located into a medium having local density of states different than the isotropic case. Furthermore, our finite-difference time-domain (FDTD) simulation shows the presence of localized spots at metal–air boundaries and corners, having intense electric field. The enhanced plasmonic field and local non-equilibrium could induce a strong thermally stimulated emission and may be the cause of our unusual observation.

415205

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Oxide semiconductors are considered to be one of the forefront candidates for the new generation, high-performance electronics. However, one of the major limitations for oxide electronics is the scarcity of an equally good hole-conducting semiconductor, which can provide identical performance for the p-type metal oxide semiconductor field-effect transistors as compared to their electron conducting counterparts. In this quest, here we present a bulk synthesis method for single crystalline cuprous oxide (Cu2O) nanowires, their chemical and morphological characterization and suitability as active channel material in electrolyte-gated, low-power, field-effect transistors (FETs) for portable and flexible logic circuits. The bulk synthesis method used in the present study includes two steps: namely hydrothermal synthesis of the nanowires and the removal of the surface organic contaminants. The surface treated nanowires are then dispersed on a receiver substrate where the passive electrodes are structured, followed by printing of a composite solid polymer electrolyte (CSPE), chosen as the gate insulator. The characteristic electrical properties of individual nanowire FETs are found to be quite interesting including accumulation-mode operation and field-effect mobility of 0.15 cm2 V−1 s−1.

Patterning and nanofabrication

415301

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Highly pure metallic structures can be deposited by electron beam induced deposition and they have many important applications in different fields. The organo-metallic precursor is decomposed and deposited under the electron beam, and typically it is purified with post-irradiation in presence of O2. However, this approach limits the purification to the surface of the deposit. Therefore, 'in situ' purification during deposition using simultaneous flows of both O2 and precursor in parallel with two gas injector needles has been tested and verified. To simplify the practical arrangements, a special concentric nozzle has been designed allowing deposition and purification performed together in a single step. With this new device metallic structures with high purity can be obtained more easily, while there is no limit on the height of the structures within a practical time frame. In this work, we summarize the first results obtained for 'in situ' Au purification using this concentric nozzle, which is described in more detail, including flow simulations. The operational parameter space is explored in order to optimize the shape as well as the purity of the deposits, which are evaluated through scanning electron microscope and energy dispersive x-ray spectroscopy measurements, respectively. The observed variations are interpreted in relation to other variables, such as the deposition yield. The resistivity of purified lines is also measured, and the influence of additional post treatments as a last purification step is studied.

415302

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Patterned chromium and its compounds are crucial materials for nanoscale patterning and chromium based devices. Here we investigate how temperature can be used to control chromium etching using chlorine/oxygen gas mixtures. Oxygen/chlorine ratios between 0% and 100% and temperatures between −100 °C and +40 °C are studied. Spectroscopic ellipsometry is used to precisely measure rates, chlorination, and the thickness dependence of n and k. Working in the extremes of oxygen content (very high or very low) and lower temperatures, we find rates can be controlled to nanometers per minute. Activation energies are measured and show that etch mechanisms are both temperature and oxygen level dependent. Furthermore, we find that etching temperature can manipulate the surface chemistry. One surprising consequence is that at low oxygen levels, Etching rates increase with decreasing temperature. Preliminary feature-profile studies show the extremes of temperature and oxygen provide advantages over commonly used room temperature processing conditions. One example is with higher ion energies at −100 °C, where etching products deposit.

Energy at the nanoscale

415401

, and

SnO2 is an attractive anode material for lithium-ion batteries (LIBs) due to its high theoretical specific capacity (1491 mAh g−1), low cost, and environmental benignity. The main challenges for SnO2 anodes are their low intrinsic conductivity and poor cycling stability associated with their large volume changes during the charge and discharge process. Here, we present a simple chemical vapor deposition method to fabricate three-dimensional SnO2/carbon on Cu foam electrodes for LIBs. Such a three-dimensional electrode combines multiple advantages, including a continuous electrically conductive network, short pathways for electron transport and ion diffusion, and porous space to allow for the volume expansion of SnO2 nanoparticles. With this anode, superior electrochemical performance is achieved with a high reversible specific capacity of 1171 mAh g−1 at a current density of 100 mA g−1. A stable cycling performance as well as an excellent rate capability is also achieved. These outstanding lithium-storage properties suggest the strategy is a reliable approach for fabricating high-performance LIB electrodes.

415402

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Yttria-stabilized zirconia (YSZ) thin film electrolyte deposited by plasma enhanced atomic layer deposition (PEALD) was investigated. PEALD YSZ-based bi-layered thin film electrolyte was employed for thin film solid oxide fuel cells on nanoporous anodic aluminum oxide substrates, whose electrochemical performance was compared to the cell with sputtered YSZ-based electrolyte. The cell with PEALD YSZ electrolyte showed higher open circuit voltage (OCV) of 1.0 V and peak power density of 182 mW cm−2 at 450 °C compared to the one with sputtered YSZ electrolyte(0.88 V(OCV), 70 mW cm−2(peak power density)). High OCV and high power density of the cell with PEALD YSZ-based electrolyte is due to the reduction in ohmic and activation losses as well as the gas and electrical current tightness.

Sensing and actuating

415501

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Traumatic injury to the central nervous system is a significant health problem. There is no effective treatment available partly because of the complexity of the system. Implementation of multifunctional micro- and nano-device based combinatorial therapeutics can provide biocompatible and tunable approaches to perform on-demand release of specific drugs. This can help the damaged cells to improve neuronal survival, regeneration of axons, and their reconnection to appropriate targets. Nano-topological features induced rapid cell growth is especially important towards the design of effective platforms to facilitate damaged neural circuit reconstruction. In this study, for the first time, feasibility of neuron-like PC12 cell growth on untreated and easy to prepare nanotextured surfaces has been carried out. The PC12 neuron-like cells were cultured on micro reactive ion etched  nanotextured glass coverslips. The effect of nanotextured topology as physical cue for the growth of PC12 cells was observed exclusively, eliminating the possible influence(s) of the enhanced concentration of coated materials on the surface. The cell density was observed to increase by almost 200% on nanotextured coverslips compared to plain coverslips. The morphology study indicated that PC12 cell attachment and growth on the nanotextured substrates did not launch any apoptotic machinery of the cell. Less than 5% cells deformed and depicted condensed nuclei with apoptotic bodies on nanotextured surfaces which is typical for the normal cell handling and culture. Enhanced PC12 cell proliferation by such novel and easy to prepare substrates is not only attractive for neurite outgrowth and guidance, but may be used to increase the affinity of similar cancerous cells (ex: B35 neuroblastoma) and rapid proliferation thereafter—towards the development of combinatorial theranostics to diagnose and treat aggressive cancers like neuroblastoma.

415502

, , , and

Atomic force microscopy (AFM) cantilevers have proven to be very effective mass sensors. The attachment of a small mass to a vibrating cantilever produces a resonance frequency shift that can be monitored, providing the ability to measure mass changes down to a few molecules resolution. Nevertheless, the lack of a practical method to handle the catch and release process required for dynamic weighting of microobjects strongly hindered the application of the technology beyond proof of concept measurements. Here, a method is proposed in which FluidFM hollow cantilevers are exploited to overcome the standard limitations of AFM-based mass sensors, providing high throughput single object weighting with picogram accuracy. The extension of the dynamic models of AFM cantilevers to hollow cantilevers was discussed and the effectiveness of mass weighting in air was validated on test samples.

Materials: synthesis or self-assembly

415601

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We report the formation of nanoimprint master templates that can be used for the fabrication of bit patterned media (BPM). The template was formed by directed self-assembly, with solvent annealing, of a symmetric ABA triblock copolymer to form perpendicularly oriented lamellae on chemical patterns. We used a high-χ block copolymer, poly(2-vinyl pyridine)-block-polystyrene-block-poly(2-vinyl pyridine) to achieve smaller feature sizes than are possible with polystyrene-block-poly(methyl methacrylate). The work shows that triblock copolymers can provide a large processing window in terms of pitch commensurability. Using block-selective infiltration (atomic layer deposition with sequential long soaking/purge cycles), an alumina composite with high etch resistance was specifically incorporated into the polar and hydrophilic P2VP domains. Subsequently, the surface pattern was successfully transferred into underlying Si substrates by etching with a fluorine-containing plasma to create a nanoimprint master. The line/space pattern of the nanoimprint master met the BPM fabrication requirement of defectivity <10−3. For demonstration purposes, the nanoimprint master was used to imprint a replica pattern of photoresist on a quartz wafer.

415602

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We report the design of scaffolds containing mono-, bis-, and tris-phosphonate coordinating groups, and a polyethylene glycol chain, for stabilizing superparamagnetic iron oxide nanoparticles (SPIONs), using simple and versatile chemistry. We demonstrate that the number of anchoring phosphonate sites on the ligand influence the colloidal stability, magnetic and biological properties of SPIONs, and the latter do not solely depend on attaching moieties that can enhance their aqueous dispersion. These parameters can be tailored by the number of conjugation sites on the ligand, as evidenced from dynamic light scattering at various salt concentrations, magnetic relaxivities and cell viability studies.

415603

, , , and

Highly stable, luminescent, and printable/paintable supramolecular egg white hydrogel-based surface enhanced Raman scattering (SERS) matrix is created by an in situ synthesis of gold clusters inside a luminescent egg white hydrogel (Au-Gel). The synthesis of stable luminescent egg-white-based hydrogel, where the hydrogel can act as a three dimensional (3D) matrix, using a simple cross-linking chemistry, has promising application in the biomedical field including in 3D cell culturing. Furthermore, this functional hydrogel is demonstrated for micromolar-level detection of Rhodamine 6G using the SERS technique, where Au-Gel is painted over a flexible cellulose pad.

Materials: properties, characterization or tools

415701

, , , , and

One-dimensional (1D) magnetic nanostructures with high thermal stability have important industrial applications, but their fabrication remains a big challenge. Herein we demonstrate a scalable approach for the preparation of stable 1D γ-Fe2O3@carbon, which is also applicable for other metal oxide-core and carbon-shell nanostructures, such as 1D TiO2@carbon. One-dimensional ferric oxyhydroxide (α-FeO(OH)) was initially prepared by a hydrothermal method, followed by carbon coating through hydrothermal treatment of the resulting metal oxide in glucose solution. After calcination in N2 gas at 500 °C and subsequent exposure to air, the initial carbon-coated 1D α-Fe2O3 was converted to 1D γ-Fe2O3@carbon, which was very stable without any observed changes even after 1.5 years of storage under ambient conditions. The materials were then used as adsorbents and found to be highly selective towards Au (III) adsorption, of which the maximum adsorption capacity is about 600 mg Au/g sorbent (1132 mg Au/g carbon). The spent sorbent containing Au after adsorption can be readily collected by applying a magnetic field due to the presence of the magnetic core, and the adsorbed Au particles are subsequently recovered after the combustion and dissolution of the sorbent. This work demonstrates not only a facile approach to the fabrication of robust 1D magnetic materials with a stable carbon shell, but also a possible cyanide-free process for the fast and selective recovery of gold from electronic waste and industrial water.

415702

, , , , and

Accumulation of amyloid fibrils is one of the likely key factors leading to the development of Alzheimer's disease and other amyloidosis associated diseases. Magnetic nanoparticles (NPs) have been developed as promising medical materials for many medical applications. In this study, we have explored the effects of Fe3O4 NPs on the fibrillogenesis process of insulin fibrils. When Fe3O4 NPs were co-incubated with insulin, Fe3O4 NPs had no effect on the structural transformation into amyloid-like fibrils but had higher affinity toward insulin fibrils. We demonstrated that the zeta potential of insulin fibrils and Fe3O4 NPs were both positive, suggesting the binding forces between Fe3O4 NPs and insulin fibrils were van der Waals forces but not surface charge. Moreover, a different amount of Fe3O4 NPs added had no effect on secondary structural changes of insulin fibrils. These results propose the potential use of Fe3O4 NPs as therapeutic agents against diseases related to protein aggregation or contrast agents for magnetic resonance imaging.

415703

, and

The rapid development of nanoscience and nanotechnology has raised many fundamental questions that significantly impede progress in these fields. In particular, understanding the physicochemical processes at the interface in aqueous solvents requires the development and application of efficient and accurate methods. In the present work we evaluate the electrostatic contribution to the energy of model protein–ceramic complex formation in an aqueous solvent. We apply a non-local (NL) electrostatic approach that accounts for the effects of the short-range structure of the solvent on the electrostatic interactions of the interfacial systems. In this approach the aqueous solvent is considered as a non-ionic liquid, with the rigid and strongly correlated dipoles of the water molecules. We have found that an ordered interfacial aqueous solvent layer at the protein– and ceramic–solvent interfaces reduces the charging energy of both the ceramic and the protein in the solvent, and significantly increases the electrostatic contribution to their association into a complex. This contribution in the presented NL approach was found to be significantly shifted with respect to the classical model at any dielectric constant value of the ceramics. This implies a significant increase of the adsorption energy in the protein–ceramic complex formation for any ceramic material. We show that for several biocompatible ceramics (for example HfO2, ZrO2, and Ta2O5) the above effect predicts electrostatically induced protein–ceramic complex formation. However, in the framework of the classical continuum electrostatic model (the aqueous solvent as a uniform dielectric medium with a high dielectric constant ∼80) the above ceramics cannot be considered as suitable for electrostatically induced complex formation. Our results also show that the protein–ceramic electrostatic interactions can be strong enough to compensate for the unfavorable desolvation effect in the process of protein–ceramic complex formation.

415704

, , , and

Here, we present the successful fabrication of Te/TiS2 heterostructure nanocables with enhanced thermoelectric (TE) performance by a two-step route (a facile solvothermal approach for Te nanowires and then the Te nanowires are used as templates for the controllable growth of the Te/TiS2 nanocables), which is scalable for practical nanodevice applications. The heterostructure nanocables of different sizes can be prepared by varying the synthetic composition. Measurements of the Seebeck coefficient (S), electrical conductivity (σ), and thermal conductivity (κ) are carried out on the same nanowires over a temperature range of 2–350 K. The heterostructure nanocables show an ultrahigh power factor (S2σ) with a maximum value of 0.58 Wm−1 K−2, which comes from a high electrical conductivity and a strongly enhanced Seebeck coefficient. The figure of merit (ZT) can reach 1.91 at room temperature from a single nanocable with a diameter of 60 nm, which is thought to contribute to the formation of the hetero-phase core/shell structure. These results are expected to open up new application possibilities in nanoscale TE devices based on individual Te/TiS2 heterostructure nanocables.

415705

, , , , and

Electrostatic modes of atomic force microscopy have shown to be non-destructive and relatively simple methods for imaging conductors embedded in insulating polymers. Here we use electrostatic force microscopy to image the dispersion of carbon nanotubes in a latex-based conductive composite, which brings forth features not observed in previously studied systems employing linear polymer films. A fixed-potential model of the probe-nanotube electrostatics is presented which in principle gives access to the conductive nanoparticle's depth and radius, and the polymer film dielectric constant. Comparing this model to the data results in nanotube depths that appear to be slightly above the film–air interface. This result suggests that water-mediated charge build-up at the film–air interface may be the source of electrostatic phase contrast in ambient conditions.

415706

, , , , , and

In this research, novel ultrafiltration nanocomposite membranes were prepared by incorporating self-synthesized nanoporous titanium dioxide (NTiO2) nanoparticles into polysulfone. The surface of the nanoparticle was treated with a silane-based modifier to improve its distribution in the host polymer. Atomic-force microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy, Brunauer–Emmett–Teller, transmission electron microscopy, energy-dispersive x-ray spectroscopy, porosity and contact angle tests were conducted to characterize the properties of the particles as well as the fabricated nanocomposite membranes. The effects of the nanoparticle incorporation were evaluated by conducting ultrafiltration experiments. It was reported that the membrane pure water flux was increased with increasing NTiO2 loading owing to the high porosity of the nanoparticles embedded and/or formation of enlarged pores upon addition of them. The antifouling capacity of the membranes was also tested by ultrafiltration of bovine serum albumin fouling solution. It was found that both water flux and antifouling capacity tended to reach desired level if the NTiO2 added was at optimized loading.

415707

, , and

A visualization technique of subsurface features with a nanometer-scale spatial resolution is strongly demanded. Some research groups have demonstrated the visualization of subsurface features using various techniques based on atomic force microscopy. However, the imaging mechanisms have not yet been fully understood. In this study, we demonstrated the visualization of subsurface Au nanoparticles buried in a polymer matrix 900 nm from the surface using two techniques; i.e., resonance tracking atomic force acoustic microscopy and contact resonance spectroscopy. It was clarified that the subsurface features were visualized by the two techniques as the area with a higher contact resonance frequency and a higher Q-factor than those in the surrounding area, which suggests that the visualization is realized by the variation of the contact stiffness and damping of the polymer matrix due to the existence of the buried nanoparticles.

415708

, , , , , , , , , et al

Plasmonic resonant cavities are capable of confining light at the nanoscale, resulting in both enhanced local electromagnetic fields and lower mode volumes. However, conventional plasmonic resonant cavities possess large Ohmic losses at metal-dielectric interfaces. Plasmonic near-field coupling plays a key role in a design of photonic components based on the resonant cavities because of the possibility to reduce losses. Here, we study the plasmonic near-field coupling in the silver nanorod metamaterials treated as resonant nanostructured optical cavities. Reflectance measurements reveal the existence of multiple resonance modes of the nanorod metamaterials, which is consistent with our theoretical analysis. Furthermore, our numerical simulations show that the electric field at the longitudinal resonances forms standing waves in the nanocavities due to the near-field coupling between the adjacent nanorods, and a new hybrid mode emerges due to a coupling between nanorods and a gold-film substrate. We demonstrate that this coupling can be controlled by changing the gap between the silver nanorod array and gold substrate.

415709

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Frequency modulation atomic force microscopy (FM-AFM) experiments were performed on the calcite (10$\bar{1}$4) surface in pure water, and a detailed analysis was made of the 2D images at a variety of frequency setpoints. We observed eight different contrast patterns that reproducibly appeared in different experiments and with different measurement parameters. We then performed systematic free energy calculations of the same system using atomistic molecular dynamics to obtain an effective force field for the tip-surface interaction. By using this force field in a virtual AFM simulation we found that each experimental contrast could be reproduced in our simulations by changing the setpoint, regardless of the experimental parameters. This approach offers a generic method for understanding the wide variety of contrast patterns seen on the calcite surface in water, and is generally applicable to AFM imaging in liquids.

415710

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In contrast to the conventional method that obtains a high fracture strength of tungsten carbide–cobalt (WC–Co) cemented carbides by reducing WC grain size to near-nano or nanoscale, a new approach has been developed to achieve ultrahigh fracture strength by strengthening the WC grains through precipitate reinforcement. The cemented carbides were prepared by liquid-state sintering the in situ synthesized WC–Co composite powders with a little excess carbon and pre-milled Cr3C2 particles having different size scales. It was found that the nanoscale dispersed particles precipitate in the WC grains, which mainly have a coherent or semi-coherent interface with the matrix. The pinning effect of the nanoparticles on the motion of dislocations within the WC grains was observed. The mechanisms for the precipitation of nanoparticles in the WC grains were discussed, based on which a new method to enhance the resistance against the transgranular fracture of cemented carbides was proposed.

415711

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The local modification of intermolecular interactions in nickel-phthalocyanine molecules (NiPCs) is investigated on an Au(111) substrate using scanning tunneling microscopy. When the molecules are physisorbed on the substrate, they repel each other due to induced charge dipole moments. However, when the NiPC is chemisorbed on the substrate through the dehydrogenation of one of its ligands by a bias pulse, we find that a nearby physisorbed NiPC is attracted to the dehydrogenated ligand and trapped. Using our experimental results in combination with density functional theory calculations, we show that the observed attraction can be ascribed to the local charge redistribution around the dehydrogenated ligand of the chemisorbed NiPC. Furthermore, we demonstrate that desorption of the attracted NiPC from the trapped site can be readily controlled by changing the density of NiPCs around the dehydrogenated ligand.

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