Scalable Optical Nose Realized with a Chemiresistively Modulated Light-Emitter Array.

Biological olfaction relies on a large number of receptors that function as sensors to detect gaseous molecules. It is challenging to realize artificial olfactory systems that contain similarly large numbers of sensory materials. It is shown that combinatorial materials processing with vapor deposition can be used to fabricate large arrays of distinct chemiresistive sensing materials. By combining these with light-emitting diodes, an array of chemiresistively-modulated light-emitting diodes, or ChemLEDs, that permit a simultaneous optical read-out in response to an analyte is obtained. The optical nose uses a common voltage source and ground for all sensing elements and thus eliminates the need for complex wiring of individual sensors. This optical nose contains one hundred ChemLEDs and generates unique light patterns in response to gases and their mixtures. Optical pattern recognition methods enable the quantitative prediction of the corresponding concentrations and compositions, thereby paving the way for massively parallel artificial olfactory systems. ChemLEDs open the possibility to explore demanding gas sensing applications, including in environmental, food quality monitoring, and potentially diagnostic settings.

Electron Beam Induced Circularly Polarized Light Emission of Chiral Gold Nanohelices.

Chiral plasmonic nanostructures possess a chiroptical response orders of magnitude stronger than that of natural biomolecular systems, making them highly promising for a wide range of biochemical, medical, and physical applications. Despite extensive efforts to artificially create and tune the chiroptical properties of chiral nanostructures through compositional and geometrical modifications, a fundamental understanding of their underlying mechanisms remains limited. In this study, we present a comprehensive investigation of individual gold nanohelices by using advanced analytical electron microscopy techniques. Our results, as determined by angle-resolved cathodoluminescence polarimetry measurements, reveal a strong correlation between the circular polarization state of the emitted far-field radiation and the handedness of the chiral nanostructure in terms of both its dominant circularity and directional intensity distribution. Further analyses, including electron energy-loss measurements and numerical simulations, demonstrate that this correlation is driven by longitudinal plasmonic modes that oscillate along the helical windings, much like straight nanorods of equal strength and length. However, due to the three-dimensional shape of the structures, these longitudinal modes induce dipolar transverse modes with charge oscillations along the short axis of the helices for certain resonance energies. Their radiative decay leads to observed emission in the visible range. Our findings provide insight into the radiative properties and underlying mechanisms of chiral plasmonic nanostructures and enable their future development and application in a wide range of fields, such as nano-optics, metamaterials, molecular physics, biochemistry, and, most promising, chiral sensing via plasmonically enhanced chiral optical spectroscopy techniques.

Precise electrokinetic position and three-dimensional orientation control of a nanowire bioprobe in solution.

Owing to Brownian-motion effects, the precise manipulation of individual micro- and nanoparticles in solution is challenging. Therefore, scanning-probe-based techniques, such as atomic force microscopy, attach particles to cantilevers to enable their use as nanoprobes. Here we demonstrate a versatile electrokinetic trap that simultaneously controls the two-dimensional position with a precision of 20 nm and 0.5° in the three-dimensional orientation of an untethered nanowire, as small as 300 nm in length, under an optical microscope. The method permits the active transport of nanowires with a speed-dependent accuracy reaching 90 nm at 2.7 µm s-1. It also allows for their synchronous three-dimensional alignment and rotation during translocation along complex trajectories. We use the electrokinetic trap to accurately move a nanoprobe and stably position it on the surface of a single bacterial cell for sensing secreted metabolites for extended periods. The precision-controlled manipulation underpins developing nanorobotic tools for assembly, micromanipulation and biological measurements with subcellular resolution.

Thermal treatment of petroleum-contaminated marine sediment according to oxygen availability and temperature: Product quality as a potential plant-growth medium.

The sustainable management of dredged sediment from contaminated sites needs to consider the end-use of the treated sediment. In this regard, modifying conventional sediment treatment techniques to generate a product that is suitable for a range of terrestrial uses is necessary. In the present study, we evaluated the product quality of treated sediment as a potential plant-growth medium following the thermal treatment of marine sediment contaminated by petroleum. The contaminated sediment was subject to thermal treatment at temperatures of 300, 400, or 500 °C, and no, low, or moderate oxygen availability, and the resulting treated sediment was analyzed in terms of its bulk properties, spectroscopic properties, organic contaminants, water-soluble salts and organic matter, and the leachability and extractability of heavy metals. All operational combinations for the treatment process reduced the total petroleum hydrocarbon content of the sediment from 4922 mg kg-1 to lower than 50 mg kg-1. The thermal treatment process stabilized the heavy metals in the sediment, reducing the zinc and copper concentration by up to 58.9% and 89.6%, respectively, in the leachate from the toxicity characteristic leaching procedure. The hydrophilic organic and/or sulfate salt byproducts of the treatment were phytotoxic, but these can easily be removed by washing the sediment with water. By combining the sediment analysis results with experimental data from barley germination and early-growth tests, the end product was found to be of higher quality when higher temperatures and lower oxygen availability were employed in the treatment process. These findings demonstrate that it is possible to retain the natural organic resources of the original sediment by optimizing the thermal treatment, thus ensuring a suitably high product quality for use as a plant-growth medium.

Dry Synthesis of Pure and Ultrathin Nanoporous Metallic Films.

Nanoporous metals possess unique properties attributed to their high surface area and interconnected nanoscale ligaments. They are mostly fabricated by wet synthetic methods that are not universal to various metals and not free from impurities due to solution-based etching processes. Here, we demonstrate that the plasma treatment of metal nanoparticles formed by physical vapor deposition is a general route to form such films with many metals including the non-noble ones. The resultant nanoporous metallic films are free of impurities and possess highly curved ligaments and nanopores. The metal films are ultrathin, yet remarkably robust and very well connected, and thus are highly promising for various applications such as transparent conducting electrodes.

Dense Arrays of Nanohelices: Raman Scattering from Achiral Molecules Reveals the Near-Field Enhancements at Chiral Metasurfaces.

Against the background of the current healthcare and climate emergencies, surface enhanced Raman scattering (SERS) is becoming a highly topical technique for identifying and fingerprinting molecules, e.g., within viruses, bacteria, drugs, and atmospheric aerosols. Crucial for SERS is the need for substrates with strong and reproducible enhancements of the Raman signal over large areas and with a low fabrication cost. Here, dense arrays of plasmonic nanohelices (≈100 nm in length), which are of interest for many advanced nanophotonics applications, are investigated, and they are shown to present excellent SERS properties. As an illustration, two new ways to probe near-field enhancement generated with circular polarization at chiral metasurfaces are presented, first using the Raman spectra of achiral molecules (crystal violet) and second using a single, element-specific, achiral molecular vibrational mode (i.e., a single Raman peak). The nanohelices can be fabricated over large areas at a low cost and they provide strong, robust and uniform Raman enhancement. It is anticipated that these advanced materials will find broad applications in surface enhanced Raman spectroscopies and material science.

Large Area Patterning of Nanoparticles and Nanostructures: Current Status and Future Prospects.

Nanoparticles possess exceptional optical, magnetic, electrical, and chemical properties. Several applications, ranging from surfaces for optical displays and electronic devices, to energy conversion, require large-area patterns of nanoparticles. Often, it is crucial to maintain a defined arrangement and spacing between nanoparticles to obtain a consistent and uniform surface response. In the majority of the established patterning methods, the pattern is written and formed, which is slow and not scalable. Some parallel techniques, forming all points of the pattern simultaneously, have therefore emerged. These methods can be used to quickly assemble nanoparticles and nanostructures on large-area substrates into well-ordered patterns. Here, we review these parallel methods, the materials that have been processed by them, and the types of particles that can be used with each method. We also emphasize the maximal substrate areas that each method can pattern and the distances between particles. Finally, we point out the advantages and disadvantages of each method, as well as the challenges that still need to be addressed to enable facile, on-demand large-area nanopatterning.

Tailoring Binding Abilities by Incorporating Oxophilic Transition Metals on 3D Nanostructured Ni Arrays for Accelerated Alkaline Hydrogen Evolution Reaction.

Developing efficient and inexpensive electrocatalysts for the hydrogen evolution reaction (HER) in alkaline water electrolysis plays a key role for renewable hydrogen energy technology. The slow reaction kinetics of HER in alkaline solutions, however, has hampered advances in high-performance hydrogen production. Herein, we investigated the trends in HER activity with respect to the binding energies of Ni-based thin film catalysts by incorporating a series of oxophilic transition metal atoms. It was found that the doping of oxophilic atoms enables the modulation of binding abilities of hydrogen and hydroxyl ions on the Ni surfaces, leading to the first establishment of a volcano relation between OH-binding energies and alkaline HER activities. In particular, Cr-incorporated Ni catalyst shows optimized OH-binding as well as H-binding energies for facilitating water dissociation and improving HER activity in alkaline media. Further enhancement of catalytic performance was achieved by introducing an array of three-dimensional (3D) Ni nanohelixes (NHs) that provide abundant surface active sites and effective channels for charge transfer and mass transport. The Cr dopants incorporated into the Ni NHs accelerate the dissociative adsorption process of water, resulting in remarkably enhanced catalytic activities in alkaline medium. Our approach can provide a rational design strategy and experimental methodology toward efficient bimetallic electrocatalysts for alkaline HER using earth-abundant elements.

Effects of treatment agents during acid washing and pH neutralization on the fertility of heavy metal-impacted dredged marine sediment as plant-growing soil.

The present study was aimed at investigating the effects of different acids and pH neutralizers applied to dredged marine sediment for the treatment of heavy metals, and the resulting influence on the sediment quality as a plant growth medium. The inspection of barley germination in the dredged marine sediment revealed that residual salts are critical plant stressors whose adverse effects exceed those exhibited by high-level heavy metals and petroleum hydrocarbons present in the sediment. Acid washing and pH neutralization reduced not only the heavy metal contents but also the sediment salinity (by factors of 6.1-9.5), resulting in 100% germination of barley. For acid-washed and calcium-oxide-neutralized sediment, the barley growth was comparable to that observed in untreated and water washed sediment despite factors of 5.2-8.0 greater sediment salinity in the former. This result represents the protective effect of residual calcium against sodium and chloride toxicity. Water washing of acid-washed and pH-neutralized sediments further enhanced barley growth owing to the reduction in osmotic pressure. This study showed the effect of different sediment-washing reagents on the product quality. It also indicated the significance of balancing the enhancement of product quality and economic cost of further treatment requirements.

Quantitative evaluation of polyethersulfone and polytetrafluoroethylene membrane sorption in a polar organic chemical integrative sampler (POCIS).

The lag effect in the polar organic chemical integrative sampler (POCIS) equipped with a polyethersulfone (PES) membrane (POCIS-PES) is a potential limitation for its application in water environments. In this study, a POCIS with a poly(tetrafluoroethylene) (PTFE) membrane (POCIS-PTFE) was investigated for circumventing membrane sorption in order to provide more reliable concentration measurements of organic contaminants. Sampler characteristics such as sampling rates (RS) and sampler-water partition coefficients (KSW) were similar for POCIS-PES and POCIS-PTFE, indicating that partitioning into Oasis HLB as the receiving phase dominates the overall partitioning from the aqueous phase to the POCIS. Membrane sorption was quantified in both laboratory and field experiments. Although POCIS-PTFE showed minor membrane sorption, the PTFE membranes were not robust enough to prevent changes in the sorption of the pollutants to the inner Oasis HLB sorbent due to biofouling. This was reflected in significant ionization effects in the electrospray ionization (ESI) source during the LC-MS/MS analysis. Despite clear differences in the ionization effects, the two POCISs types provided similar time-weighted average (CTWA) concentrations after a two-week passive sampling campaign in surface water and the outflow of a wastewater treatment plant. This study contributes to a more detailed understanding of POCIS application by providing a quantitative evaluation of membrane sorption and its associated effects in the laboratory and field.

Biocompatible Magnetic Micro- and Nanodevices: Fabrication of FePt Nanopropellers and Cell Transfection.

The application of nanoparticles for drug or gene delivery promises benefits in the form of single-cell-specific therapeutic and diagnostic capabilities. Many methods of cell transfection rely on unspecific means to increase the transport of genetic material into cells. Targeted transport is in principle possible with magnetically propelled micromotors, which allow responsive nanoscale actuation and delivery. However, many commonly used magnetic materials (e.g., Ni and Co) are not biocompatible, possess weak magnetic remanence (Fe3 O4 ), or cannot be implemented in nanofabrication schemes (NdFeB). Here, it is demonstrated that co-depositing iron (Fe) and platinum (Pt) followed by one single annealing step, without the need for solution processing, yields ferromagnetic FePt nanomotors that are noncytotoxic, biocompatible, and possess a remanence and magnetization that rival those of permanent NdFeB micromagnets. Active cell targeting and magnetic transfection of lung carcinoma cells are demonstrated using gradient-free rotating millitesla fields to drive the FePt nanopropellers. The carcinoma cells express enhanced green fluorescent protein after internalization and cell viability is unaffected by the presence of the FePt nanopropellers. The results establish FePt, prepared in the L10 phase, as a promising magnetic material for biomedical applications with superior magnetic performance, especially for micro- and nanodevices.

Comparing passive dosing and solvent spiking methods to determine the acute toxic effect of pentachlorophenol on Daphnia magna.

Pentachlorophenol (PCP) is a widespread and persistent hydrophobic organic pollutant in the environment despite its restricted public use. Risk assessment of such hydrophobic organic compounds (HOCs) is challenging because sorption and volatilization issues during toxicity test often lead to inconsistent exposure concentration. Considering the hydrophobicity of the PCP, in this study, a passive dosing format was applied by adopting a silicone O-ring as a reservoir and evaluated its applicability on the determination of PCP on Daphnia magna. Results obtained with passive dosing method were compared with that of solvent spiking method. We hypothesized that the passive dosing method may provide more reliable and accurate toxicity results than conventional solvent spiking approach. As a result, the partition coefficient of PCP between methanol and a test medium (log KMeOH:ISO) was 2.1, which enabled the maintenance of reliable exposure concentration throughout the experiment. In the acute toxicity tests, passive dosing and solvent spiking showed similar EC50 values of 576 and 485 µg/L for 24 h, and 362 and 374 µg/L for 48 h, respectively, which overlap with EC50 values of previous studies. Altogether, both methods were suitable for the acute toxicity assessment of hydrophobic PCP.

Gate-tunable gas sensing behaviors in air-stable ambipolar organic thin-film transistors.

Chemiresistive gas sensors, which exploit their electrical resistance in response to changes in nearby gas environments, usually achieve selective gas detection using multi-element sensor arrays. As large numbers of sensors are required, they often suffer from complex and high-cost fabrication. Here, we demonstrate an ambipolar organic thin-film transistor as a potential multi-gas sensing device utilizing gate-tunable gas sensing behaviors. Combining behaviors of both electron and hole carriers in a single device, the proposed device showed dynamic changes depending on gate biases and properties of target gases. As a result, the gas response as a function of gate biases exhibits a unique pattern towards a specific gas as well as its concentrations, which is very different from conventional unipolar organic thin-film transistors. In addition, our device showed an excellent air-stable characteristic compared to typical ambipolar transistors, providing great potential for practical use in the future.

Overcoming ineffective resistance modulation in p-type NiO gas sensor by nanoscale Schottky contacts.

We present a gas sensor having nanoscale Schottky contacts on an array of helical-shaped p-type NiO to overcome intrinsically ineffective resistance modulation in the bulk of p-type metal oxides upon gas exposure. The Schottky device shows an abnormal n-type sensing behavior despite using the p-type NiO under reducing gas, with the sensitivity of 142.9% at 200 ppm of hydrogen, much higher than the reference Ohmic device with 0.7% sensitivity. Based on our equivalent circuit model with the quantitative estimation of the modulations in both carrier concentration and Schottky barrier height upon gas exposure, such a high sensitivity and the abnormal sensing behavior are attributed to the predominant modulation in the barrier height at the nanoscale Schottky contacts which are uniquely designed to have top-and-bottom electrodes configuration for efficient gas adsorption and sensitive Schottky barrier height modulation.

Reversible phase modulation and hydrogen storage in multivalent VO2 epitaxial thin films.

Hydrogen, the smallest and the lightest atomic element, is reversibly incorporated into interstitial sites in vanadium dioxide (VO2), a correlated oxide with a 3d(1) electronic configuration, and induces electronic phase modulation. It is widely reported that low hydrogen concentrations stabilize the metallic phase, but the understanding of hydrogen in the high doping regime is limited. Here, we demonstrate that as many as two hydrogen atoms can be incorporated into each VO2 unit cell, and that hydrogen is reversibly absorbed into, and released from, VO2 without destroying its lattice framework. This hydrogenation process allows us to elucidate electronic phase modulation of vanadium oxyhydride, demonstrating two-step insulator (VO2)-metal (HxVO2)-insulator (HVO2) phase modulation during inter-integer d-band filling. Our finding suggests the possibility of reversible and dynamic control of topotactic phase modulation in VO2 and opens up the potential application in proton-based Mottronics and novel hydrogen storage.

Three-Dimensional Metal-Oxide Nanohelix Arrays Fabricated by Oblique Angle Deposition: Fabrication, Properties, and Applications.

Three-dimensional (3D) nanostructured thin films have attracted great attention due to their novel physical, optical, and chemical properties, providing tremendous possibilities for future multifunctional systems and for exploring new physical phenomena. Among various techniques to fabricate 3D nanostructures, oblique angle deposition (OAD) is a very promising method for producing arrays of a variety of 3D nanostructures with excellent controllability, reproducibility, low cost, and compatibility with modern micro-electronic processes. This article presents a comprehensive overview of the principle of OAD, and unique structural and optical properties of OAD-fabricated thin films including excellent crystallinity, accurate tunability of refractive indices, and strong light scattering effect which can be utilized to remarkably enhance performances of various systems such as antireflection coatings, optical filters, photoelectrodes for solar-energy-harvesting cells, and sensing layers for various sensors.

Effects of graphene oxides on soil enzyme activity and microbial biomass.

Due to recent developments in nanotechnology, nanomaterials (NMs) such as graphene oxide (GO) may enter the soil environment with mostly unknown consequences. We investigated the effects of GO on soil microbial activity in a 59-day soil incubation study. For this, high-purity GO was prepared and characterized. Soils were treated with up to 1 mg GO g(-1) soil, and the changes in the activities of 1,4-ß-glucosidase, cellobiohydrolase, xylosidase, 1,4-ß-N-acetyl glucosaminidase, and phosphatase and microbial biomass were determined. 0.5-1 mg GO g(-1) soil lowered the activity of xylosidase, 1,4-ß-N-acetyl glucosaminidase, and phosphatase by up to 50% when compared to that in the control soils up to 21 days of incubation. Microbial biomass in soils treated with GO was not significantly different from that in control soils throughout the incubation period, and the soil enzyme activity and microbial biomass were not significantly correlated in this study. Our results indicate that soil enzyme activity can be lowered by the entry of GO into soils in short term but it can be recovered afterwards.

A near single crystalline TiO2 nanohelix array: enhanced gas sensing performance and its application as a monolithically integrated electronic nose.

We present high performance gas sensors based on an array of near single crystalline TiO(2) nanohelices fabricated by rotating oblique angle deposition (OAD). The combination of large surface-to-volume ratio, extremely small size (<30 nm) comparable to the Debye length, a near single crystallinity of TiO(2) nanohelices, together with the unique top-and-bottom electrode configuration hugely improves the H(2)-sensing performance, including ∼10 times higher response at 50 ppm, approximately a factor of 5 lower detection limit, and much faster response time than the conventional TiO(2) thin film devices. Beyond such remarkable performance enhancement, the excellent compatibility of the OAD method compared with the conventional micro-fabrication technology opens a new avenue for monolithic integration of high-performance chemoresistive sensors to fabricate a simple, low cost, reliable, yet fully functional electronic nose and multi-functional smart chips for in situ environmental monitoring.