Unique gap-related SERS behaviors ofp-aminothiophenol molecules absorbed on TiO2surface in periodic TiO2/Ni nanopillar arrays.

We observed a unique interpillar gap-related surface-enhanced Raman scattering (SERS) behavior ofp-aminothiophenol (PATP) molecules from periodic TiO2nanopillar arrays with three gap sizes of 191, 297 and 401 nm, which is completely different from that on Ag and Ni nanopillar arrays. Especially, the gap-size-dependent charge-transfer (CT) resonance enhancement from TiO2/Ni has been indicated through comparisons of variation trend of SERS intensities with inter-pillar gap size between TiO2/Ni and Ag/TiO2/Ni as well as Ni nanoarrays, and been confirmed by spectra of ultraviolet-visible absorption and photoluminescence. Results demonstrate that the CT resonance enhancement is more susceptible to the change of the gap size compared with the surface plasmon resonance (SPR) enhancement in TiO2/Ni nanoarrays. Hence, SPR and CT enhancement showing different variation trend and rate with the gap size that leads to a different relative contribution of CT resonance to the overall SERS enhancement as gap size changes, and consequently results in a unique gap-related SERS behavior for TiO2/Ni nanoarrays. The present study is not only helpful for investigating SERS mechanism for semiconductors but also providing a method to design and optimize periodic metal/semiconductor SERS substrates in a controllable way.

Fabrication of Nickel Oxide Nanopillar Arrays on Flexible Electrodes for Highly Efficient Perovskite Solar Cells.

Semiconductor nanomaterials with controlled morphologies and architectures are of critical importance for high-performance optoelectronic devices. However, the fabrication of such nanomaterials on polymer-based flexible electrodes is particularly challenging due to degradation of the flexible electrodes at a high temperature. Here we report the fabrication of nickel oxide nanopillar arrays (NiO x NaPAs) on a flexible electrode by vapor deposition, which enables highly efficient perovskite solar cells (PSCs). The NiO x NaPAs exhibit an enhanced light transmittance for light harvesting, prohibit exciton recombination, promote irradiation-generated hole transport and collection, and facilitate the formation of large perovskite grains. These advantageous features result in a high efficiency of 20% and 17% for the rigid and flexible PSCs, respectively. Additionally, the NaPAs show no cracking after 500 times of bending, consistent with the mechanic simulation results. This robust fabrication opens a new opportunity for the fabrication of a large area of high-performance flexible optoelectronic devices.

Nanotopography-Promoted Formation of Axon Collateral Branches of Hippocampal Neurons.

Axon collateral branches, as a key structural motif of neurons, allow neurons to integrate information from highly interconnected, divergent networks by establishing terminal boutons. Although physical cues are generally known to have a comprehensive range of effects on neuronal development, their involvement in axonal branching remains elusive. Herein, it is demonstrated that the nanopillar arrays significantly increase the number of axon collateral branches and also promote their growth. Immunostaining and biochemical analyses indicate that the physical interactions between the nanopillars and the neurons give rise to lateral filopodia at the axon shaft via cytoskeletal changes, leading to the formation of axonal branches. This report, demonstrates that nanotopography regulates axonal branching, and provides a guideline for the design of sophisticated neuron-based devices and scaffolds for neuro-engineering.

The susceptibility of Staphylococcus aureus CIP 65.8 and Pseudomonas aeruginosa ATCC 9721 cells to the bactericidal action of nanostructured Calopteryx haemorrhoidalis damselfly wing surfaces.

Nanostructured insect wing surfaces have been reported to possess the ability to resist bacterial colonization through the mechanical rupture of bacterial cells coming into contact with the surface. In this work, the susceptibility of physiologically young, mature and old Staphylococcus aureus CIP 65.8 and Pseudomonas aeruginosa ATCC 9721 bacterial cells, to the action of the bactericidal nano-pattern of damselfly Calopteryx haemorrhoidalis wing surfaces, was investigated. The results were obtained using several surface characterization techniques including optical profilometry, scanning electron microscopy, synchrotron-sourced Fourier transform infrared microspectroscopy, water contact angle measurements and antibacterial assays. The data indicated that the attachment propensity of physiologically young S. aureus CIP 65.8T and mature P. aeruginosa ATCC 9721 bacterial cells was greater than that of the cells at other stages of growth. Both the S. aureus CIP 65.8T and P. aeruginosa ATCC 9721 cells, grown at the early (1 h) and late stationary phase (24 h), were found to be most susceptible to the action of the wings, with up to 89.7 and 61.3% as well as 97.9 and 97.1% dead cells resulting from contact with the wing surface, respectively.

Effects of Surface Topography and Cellular Biomechanics on Nanopillar-Induced Bactericidal Activity.

Bacteria are mechanically resistant biological structures that can sustain physical stress. Experimental data, however, have shown that high-aspect-ratio nanopillars deform bacterial cells upon contact. If the deformation is sufficiently large, it lyses the bacterial cell wall, ultimately leading to cell death. This has prompted a novel strategy, known as mechano-bactericide technology, to fabricate antibacterial surfaces. Although adhesion forces were originally proposed as the driving force for mechano-bactericidal action, it has been recently shown that external forces, such as capillary forces arising from an air-water interface at bacterial surfaces, produce sufficient loads to rapidly kill bacteria on nanopillars. This discovery highlights the need to theoretically examine how bacteria respond to external loads and to ascertain the key factors. In this study, we developed a finite element model approximating bacteria as elastic shells filled with cytoplasmic fluid brought into contact with an individual nanopillar or nanopillar array. This model elucidates that bacterial killing caused by external forces on nanopillars is influenced by surface topography and cell biomechanical variables, including the density and arrangement of nanopillars, in addition to the cell wall thickness and elastic modulus. Considering that surface topography is an important design parameter, we performed experiments using nanopillar arrays with precisely controlled nanopillar diameters and spacing. Consistent with model predictions, these demonstrate that nanopillars with a larger spacing increase bacterial susceptibility to mechanical puncture. The results provide salient insights into mechano-bactericidal activity and identify key design parameters for implementing this technology.

Multiple-perspective design of hollow-structured cerium-vanadium-based nanopillar arrays for enhanced overall water electrolysis.

It is critical and challenging to develop highly active and low cost bifunctional electrocatalysts for the hydrogen/oxygen evolution reaction (HER/OER) in water electrolysis. Herein, we propose cerium-vanadium-based hollow nanopillar arrays supported on nickel foam (CeV-HNA/NF) as bifunctional HER/OER electrocatalysts, which are prepared by etching the V metal-organic framework with Ce salt and then pyrolyzing. Etching results in multidimensional optimizations of electrocatalysts, covering substantial oxygen vacancies, optimized electronic configurations, and an open-type structure of hollow nanopillar arrays, which contribute to accelerating the charge transfer rate, regulating the adsorption energy of H/O-containing reaction intermediates, and fully exposing the active sites. The reconstruction of the electrocatalyst is also accelerated by Ce doping, which results in highly active hydroxy vanadium oxide interfaces. Therefore, extremely low overpotentials of 170 and 240 mV under a current density of 100 mA cm-2 are achieved for the HER and OER under alkaline conditions, respectively, with long-term stability for 300 h. An electrolysis cell with CeV-HNA/NF as both the cathode and anode delivers a small voltage of 1.53 V to achieve water electrolysis under 10 mA cm-2, accompanied by superior durability for 150 h. This design provides an innovative way to develop advanced bifunctional electrocatalysts for overall water electrolysis.

Enhanced light out-coupling of OLEDs with low haze by inserting randomly dispersed nanopillar arrays formed by lateral phase separation of polymer blends.

A simple and efficient method to fabricate light extraction layers is demonstrated by utilizing the phase separation of two polymer blends to enhance the light out-coupling efficiency of OLEDs with low haze. Polystyrene and poly(methyl methacrylate) dissolved in tetrahydrofuran are mixed and spin-coated over ITO-coated glass substrates. Nanopores and nanopillar arrays are formed through lateral phase separation of the polymer blend. The shape, size, and distribution of the patterns can be controlled through changes in the composition and thickness of the coated polymer blends. Phosphorescent OLEDs are fabricated using randomly dispersed nanopillar arrays as light extraction layers and they show a 24% enhancement in external quantum efficiency with a Lambertian emission pattern, no spectrum dependence on viewing angles, and only a small increment in the haze. With these advantages, this newly developed method can be adapted to be used for large-area, flexible substrates for lighting and display applications.

Flexible and highly ordered nanopillar electrochemical sensor for sensitive insulin evaluation.

In line with growing interest in obesity management, there has been an increase in the amount of research focused on highly sensitive analysis systems for a small number of biomarers. In this paper, we introduce the highly ordered nanopillar electrode, featuring a high aspect ratio surface area that enables enhanced electron transfer. For fabrication of the flexible electrode, gold was evaporated by electronic beam lithography on polyurethane (PU), which has high flexibility. The fabricated nanopillar is 500 nm in diameter and 1500 nm in height. Based on the highly ordered nanostructure electrode, insulin was selected as a biomarker to monitor the insulin resistance associated with obesity. To effectively analyze the insulin, the self-assembled monolayer chemical was used to introduce the enzyme catalysis-based electrochemical immunoassay, leading to the analysis of the insulin concentration range from 0.1 to 1.0 ng/mL in the real sample. The square wave voltammetry principle was used to measure HRP-based electrochemical signal both electrochemically and quantitatively. Based on the nanostructural properties of significant electrochemical behavior, we successfully analyzed insulin in the plasma sample with high sensitivity (LOD of 0.1 ng/mL) and with high reproducibility (<10%). The obtained sensitivity of nanopillar electrode is approximately 10 times (1020%) greater than that of commercial electrode. The results demonstrated that the nanopillar electrode is suitable for precise and sensitive analysis of low-level biomolecules in medical and commercial fields.

Antibacterial Nanopillar Array for an Implantable Intraocular Lens.

Postsurgical intraocular lens (IOL) infection caused by pathogenic bacteria can result in blindness and often requires a secondary operation to replace the contaminated lens. The incorporation of an antibacterial property onto the IOL surface can prevent bacterial infection and postoperative endophthalmitis. This study describes a polymeric nanopillar array (NPA) integrated onto an IOL, which captures and eradicates the bacteria by rupturing the bacterial membrane. This is accomplished by changing the behavior of the elastic nanopillars using bending, restoration, and antibacterial surface modification. The combination of the polymer coating and NPA dimensions can decrease the adhesivity of corneal endothelial cells and posterior capsule opacification without causing cytotoxicity. An ionic antibacterial polymer layer is introduced onto an NPA using an initiated chemical vapor deposition process. This improves bacterial membrane rupture efficiency by increasing the interactions between the bacteria and nanopillars and damages the bacterial membrane using quaternary ammonium compounds. The newly developed ionic polymer-coated NPA exceeds 99% antibacterial efficiency against Staphylococcus aureus, which is achieved through topological and physicochemical surface modification. Thus, this paper provides a novel, efficient strategy to prevent postoperative complications related to bacteria contamination of IOL after cataract surgery.

A Lipid-Nanopillar-Array-Based Immunosorbent Assay.

Since infectious diseases, particularly viral infections, have threatened human health and caused huge economical losses globally, a rapid, sensitive, and selective virus detection platform is highly demanded. Enzyme-linked immunosorbent assay (ELISA) with flat solid substrates has been dominantly used in detecting whole viruses for its straightforwardness and simplicity in assay protocols, but it often suffers from limited sensitivity, poor quantification range, and a time-consuming assay procedure. Here, a lipid-nanopillar-array-based immunosorbent assay (LNAIA) is developed with a nanopillar-supported lipid bilayer substrate with fluorophore-modified antibodies for rapid, sensitive, and quantitative detection of viruses. 3D nanopillar array structures and fluid antibodies with fluorophores facilitate faster and efficient target binding and rapid fluorophore localization for quick, reliable analysis on binding events with a conventional fluorescence microscopy setup. LNAIA enables quantification of H1N1 virus that targets down to 150 virus particles with 5-orders-of-magnitude dynamic range within 25 min, which cannot be achieved with conventional ELISA platforms.

Flexible nanopillar-based electrochemical sensors for genetic detection of foodborne pathogens.

Flexible and highly ordered nanopillar arrayed electrodes have brought great interest for many electrochemical applications, especially to the biosensors, because of its unique mechanical and topological properties. Herein, we report an advanced method to fabricate highly ordered nanopillar electrodes produced by soft-/photo-lithography and metal evaporation. The highly ordered nanopillar array exhibited the superior electrochemical and mechanical properties in regard with the wide space to response with electrolytes, enabling the sensitive analysis. As-prepared gold and silver electrodes on nanopillar arrays exhibit great and stable electrochemical performance to detect the amplified gene from foodborne pathogen of Escherichia coli O157:H7. Additionally, lightweight, flexible, and USB-connectable nanopillar-based electrochemical sensor platform improves the connectivity, portability, and sensitivity. Moreover, we successfully confirm the performance of genetic analysis using real food, specially designed intercalator, and amplified gene from foodborne pathogens with high reproducibility (6% standard deviation) and sensitivity (10 × 1.01 CFU) within 25 s based on the square wave voltammetry principle. This study confirmed excellent mechanical and chemical characteristics of nanopillar electrodes have a great and considerable electrochemical activity to apply as genetic biosensor platform in the fields of point-of-care testing (POCT).

Controllable Fabrication of Non-Close-Packed Colloidal Nanoparticle Arrays by Ion Beam Etching.

Polystyrene (PS) nanoparticle films with non-close-packed arrays were prepared by using ion beam etching technology. The effects of etching time, beam current, and voltage on the size reduction of PS particles were well investigated. A slow etching rate, about 9.2 nm/min, is obtained for the nanospheres with the diameter of 100 nm. The rate does not maintain constant with increasing the etching time. This may result from the thermal energy accumulated gradually in a long-time bombardment of ion beam. The etching rate increases nonlinearly with the increase of beam current, while it increases firstly then reach its saturation with the increase of beam voltage. The diameter of PS nanoparticles can be controlled in the range from 34 to 88 nm. Based on the non-close-packed arrays of PS nanoparticles, the ordered silicon (Si) nanopillars with their average diameter of 54 nm are fabricated by employing metal-assisted chemical etching technique. Our results pave an effective way to fabricate the ordered nanostructures with the size less than 100 nm.

Flexible Lithium Ferrite Nanopillar Arrays for Bending Stable Microwave Magnetism.

Recent development in magnetic nanostructures has promoted flexible electronics into the application of integrated devices. However, the magnetic properties of flexible devices strongly depend on the bending states. In order to realize the design of new flexible devices driven by an external field, the first step is to make the magnetic properties insensitive to the bending. Herein, a series of LiFe5O8 nanopillar arrays were fabricated, whose microwave magnetic properties can be modulated by tuning the nanostructure. This work demonstrates that nanostructure engineering is useful to control the bending sensitivity of microwave magnetism and further design stable flexible devices.

Biofunctionalized 3D Nanopillar Arrays Fostering Cell Guidance and Promoting Synapse Stability and Neuronal Activity in Networks.

A controlled geometry of in vitro neuronal networks allows investigation of the cellular mechanisms that underlie neuron-to-neuron and neuron-extracellular matrix interactions, which are essential to biomedical research. Herein, we report a selective guidance of primary hippocampal neurons by using arrays of three-dimensional vertical nanopillars (NPs) functionalized with a specific adhesion-promoting molecule-poly-dl-ornithine (PDLO). We show that 90% of neuronal cells are guided exclusively on the combinatorial PDLO/NP substrate. Moreover, we demonstrate the influence of the interplay between nanostructures and neurons on synapse formation and maturation, resulting in increased expression of postsynaptic density-95 protein and enhanced network cellular activity conferred by the endogenous c-fos expression. Successful guidance to foster synapse stability and cellular activity on multilevel cues of surface topography and chemical functionalization suggests the potential to devise technologies to control neuronal growth on nanostructures for tissue engineering, neuroprostheses, and drug development.