Nanostructured Substrates Research Articles

Dual nanofibrous bioactive coating and antimicrobial surface treatment for infection resistant titanium implants

Failures of biomedical implants due to implant-related infections and implant loosening remains a major concern in orthopaedic fixations. The current work aims to address the issues by examining the effect of dual interaction i.e surface modification and surface coatings on orthopaedic implant materials, i.e. commercially pure titanium (cpTi). The cpTi surface was initially modified with piranha solution (H2SO4 + H2O2) to create an antibacterial surface. Further, the biological properties similar to bone tissue were improved by electrospun coating on the piranha treated substrate with poly(ε-caprolactone)(PCL)/hydroxyapatite (HA) composite nanofibers. The PCL/HA composite nanofibers have been characterized using SEM, XRD, EDS contact angle measurements, and FTIR spectroscopy. The coating adhesion of PCL/HA on cpTi was evaluated by cross-cut tape test (ASTM D3359-09). The newly fabricated substrates showed favourable properties and higher wettability. The antibacterial tests on piranha treated nanostructured substrates also confirmed a substantial reduction in bacterial growth over large areas. Cellular interactive responses such as adhesive and proliferation of osteosarcoma MG-63 cell lines has also demonstrated that presence of PCL/HA electrospun coating on the modified surface have improved the biological properties. The currently developed piranha treated and PCL/HA nanocomposite coated cpTi substrates seems to be a promising method to obtain both antibacterial and bioactive titanium surfaces.

Enhanced UV Flexible Photodetectors and Photocatalysts Based on TiO2 Nanoplatforms

In this study, titanium dioxide (TiO2) nanostructured films were synthesized under microwave irradiation through low temperature synthesis (80 °C) and integrated in ultraviolet (UV) photodetectors and as photocatalysts. Bacterial nanocellulose (BNC), tracing paper, and polyester film were tested as substrates, since they are inexpensive, flexible, recyclable, lightweight, and when associated to low temperature synthesis and absence of a seed layer, they become suitable for several low-cost applications. The nanostructured TiO2 films and substrates were structurally characterized by scanning electron microscopy coupled with energy dispersive X-ray spectroscopy, X-ray diffraction, and Raman spectroscopy. The optical properties of all materials were investigated. The TiO2 nanostructured films were implemented as a photoactive layer of UV photodetectors and demonstrated significant increase of conductance upon exposed to UV irradiation. The photodetection behaviour of each material was investigated by in-situ Kelvin probe force microscopy experiments, in which the contact potential difference varied under dark or UV irradiation conditions, demonstrating higher shift for the BNC-based UV photodetector. Photocatalytic activity of the films was assessed from rhodamine B degradation under solar radiation, and BNC based devices revealed to be the best photocatalyst. The structural characteristics of the TiO2 films and substrates were correlated to the differences in the UV photodetection and photocatalytic performances.

Trade-off between Photon Management Efficacy and Material Quality in Thin-Film Solar Cells on Nanostructured Substrates of High Aspect Ratio Structures

Although texturing of the transparent electrode of thin-film solar cells has long been used to enhance light absorption via light trapping, such texturing has involved low aspect ratio features. With the recent development of nanotechnology, nanostructured substrates enable improved light trapping and enhanced optical absorption via resonances, a process known as photon management, in thin-film solar cells. Despite the progress made in the development of photon management in thin-film solar cells using nanostructures substrates, the structural integrity of the thin-film solar cells deposited onto such nanostructured substrates is rarely considered. Here, we report the observation of the reduction in the open circuit voltage of amorphous silicon solar cells deposited onto a nanostructured substrate with increasing areal number density of high aspect ratio structures. For a nanostructured substrate with the areal number density of such nanostructures increasing in correlation with the distance from one edge of the substrate, a correlation between the open circuit voltage reduction and the increase of the areal number density of high aspect ratio nanostructures of the front electrode of the small-size amorphous silicon solar cells deposited onto different regions of the substrate with graded nanostructure density indicates the effect of the surface morphology on the material quality, i.e., a trade-off between photon management efficacy and material quality. This observed trade-off highlights the importance of optimizing the morphology of the nanostructured substrate to ensure conformal deposition of the thin-film solar cell.

Molecular Structure and Solvent Factors Influencing SERS on Planar Gold Substrates

Adsorption of analytes on surface enhanced Raman scattering (SERS) active nanometallic substrates is influenced by a variety of factors, including analyte–metal interactions, analyte–solvent interactions, and competition for the limited number of available sites on the surface. In this article, we present a study of the effects of solubility on the binding of analytes to metallic substrates as well as an equation to describe the effect of these interactions on the observed SERS signal. A variety of solvents are used to demonstrate the effect on binding of 1,2-bis(4-pyridyl)-ethylene and thiophenol to nanostructured gold SERS substrates. These solvents include mixtures of ethanol/water and acetonitrile/water with different ratios of organic/water fractions. In our previous work, two types of sites were observed on nanostructured gold substrates—nucleophilic and electrophilic—which tend to bind with analytes that are either electron poor or electron rich, respectively. The present study shows that the compo...

Aluminum-doped ZnO thin films deposited on flat and nanostructured glass substrates: Quality and performance for applications in organic solar cells

Transparent conductive aluminum-doped zinc oxide (AZO) thin films were deposited on a flat and nanostructured borosilicate glass substrates by using DC-magnetron sputtering. The aluminum doping concentration was kept at 3.3 wt% and the film thickness (100–400 nm) was varied. The thin films were then annealed at 250 °C for 1 h in nitrogen and/or argon atmosphere, respectively. AZO thin films exhibited hexagonal wurtzite structure of ZnO with an intense (0 0 2) diffraction peak, indicating that they have c-axis preferred orientation. Optical transmittance was observed to be greater than 80% in the visible range for films deposited on both flat and nanostructured glass substrates. The lowest resistivity of 9.7 × 10−4 Ω cm was observed for AZO film of 400 nm thickness on flat glass substrate, annealed in Nitrogen atmosphere. The power conversion efficiency (PCE) of 0.27% and 2.24% were recorded for organic solar cell devices based on AZO deposited on nanostructured and flat borosilicate glass, respectively. In comparison with the latter, the PCE of ITO based device was recorded to be 3.17%. Due to their good optical and electrical properties, AZO thin films are promising candidates as transparent electrodes in organic solar cells.

Protein-Metal Interactions Probed by SERS: Lysozyme on Nanostructured Gold Surface

Surface-enhanced Raman scattering is a well-established technique for molecular detection at low concentration, which is becoming increasingly popular in the field of biotechnology and health sciences. Since the process is understood in depth, the technique is becoming reliable. In this contribution, we consider another aspect of SERS besides molecular detection, focusing on the binding mechanisms of a complex system such as a protein to the noble metal substrates required by the technique itself. We also show that using a solid nanostructured substrate produced by controlled pulsed laser deposition SERS enables label-free detection of a protein. This is checked on lysozyme as a well-known prototype. Use of solid substrates with controlled morphology proves advantageous over colloidal systems for SERS applications. Moreover, such substrates are superior in terms of shelf life, packaging and ease of shipment.

Negative ion laser desorption/ionization time-of-flight mass spectrometric analysis of small molecules by using nanostructured substrate as matrices.

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) is an excellent analytical technique for rapid and sensitive analysis of macromolecules such as polymers and proteins. However, the main drawback of MALDI-TOF MS is its difficulty to detect small molecules with mass below 700 Da because of the intensive interference from MALDI matrix in the low mass region. In recent years there has been considerable interest in developing matrix-free laser desorption/ionization by using nanostructured substrates to substitute the conventional organic matrices, which is often referred as surface-assisted laser desorption/ionization time-of-flight mass spectrometry (SALDI-TOF MS). Despite these attractive features, most of the current SALDI-TOF MS for the analysis of small molecules employ positive ion mode, which is subjected to produce multiple alkali metal adducts, and thus increases the complexity of the analysis. Different from the complicated adducts produced in positive ion mode, mass spectra obtained in negative ion mode are featured by deprotonated ion peaks without matrix interference, which simplifies the interpretation of mass spectra and detection of unknown. In this review, we critically survey recent advances in nanostructured substrates for negative ion LDI-TOF MS analysis of small molecules in the last 5 years. Special emphasis is placed on the preparation of the nanostructured substrates and the results achieved in negative ion SALDI-MS. In addition, a variety of promising applications including environmental, biological, and clinical analysis are introduced. The ionization mechanism of negative ionization is briefly discussed.

Blade Coating Aligned, High-Performance, Semiconducting-Polymer Transistors

Recent demonstration of mobilities in excess of 10 cm2 V–1 s–1 have energized research in solution deposition of polymers for thin film transistor applications. Due to the lamella motif of most soluble, semiconducting polymers, the local mobility is intrinsically anisotropic. Therefore, fabrication of aligned films is of interest for optimization of device performance. Many techniques have been developed to control film alignment, including solution deposition via directed flows and deposition on topologically structured substrates. We report device and detailed structural analysis (ultraviolet–visible absorption, IR absorption, near-edge X-ray absorption (NEXAFS), grazing incidence X-ray diffraction, and atomic force microscopy) results from blade coating two high performing semiconducting polymers on unpatterned and nanostructured substrates. Blade coating exhibits two distinct operational regimes: the Landau–Levich or horizontal dip coating regime and the evaporative regime. We find that in the evapora...

Evaluation of the pH-sensitive swelling of a hydrogel by means of a plasmonic sensor substrate

Abstract. The inline monitoring of parameters in aqueous liquids is facing an increasing demand in many different application areas. Hydrogels with pH-induced swelling and deswelling behavior offer a means to measure pH in such liquids. Here we investigate the optical interrogation of a pH-sensitive hydrogel which can be applied in the physiological pH range. For this, a nanostructured gold substrate supporting surface plasmon oscillations is coated with a HPMA/DMAEMA/TEGDMA/EG hydrogel. The gel swells in the pH range under investigation (here 4.5 to 6.5), and the resulting refractive index changes subsequently lead to a spectral shift of the plasmon resonance of the gold nanostructure. The spectral resonance position is determined from optical transmittance spectra of the sensor substrates, and the initial results for our hydrogel reported here indicate a nearly linear dependence between the swelling state and the plasmon resonance wavelength.

Bulk and Surface Morphologies of ABC Miktoarm Star Terpolymers Composed of PDMS, PI, and PMMA Arms

DIM miktoarm star copolymers, composed of polydimethylsiloxane [D], poly(1,4-isoprene) [I], and poly(methyl methacrylate) [M], were synthesized using a newly developed linking methodology with 4-allyl-1,1-diphenylethylene as a linking agent. The equilibrium bulk morphologies of the DIM stars were found to range from [6.6.6] tiling patterns to alternating lamellar and alternating cylindrical morphologies, as determined experimentally by small-angle X-ray scattering and transmission electron microscopy and confirmed by dissipative particle dynamics and self-consistent field theory based arguments. The thin film morphologies, which differ from those found in the bulk, were identified by scanning electron microscopy, coupled with oxygen plasma etching. Square arrays of the PDMS nanodots and empty core cylinders were formed on silica after oxygen plasma removal of the poly(1,4-isoprene) and poly(methyl methacrylate) which generated nanostructured substrates decorated with these features readily observable.

NanoVelcro rare-cell assays for detection and characterization of circulating tumor cells.

Circulating tumor cells (CTCs) are cancer cells shredded from either a primary tumor or a metastatic site and circulate in the blood as the potential cellular origin of metastasis. By detecting and analyzing CTCs, we will be able to noninvasively monitor disease progression in individual cancer patients and obtain insightful information for assessing disease status, thus realizing the concept of "tumor liquid biopsy". However, it is technically challenging to identify CTCs in patient blood samples because of the extremely low abundance of CTCs among a large number of hematologic cells. In order to address this challenge, our research team at UCLA pioneered a unique concept of "NanoVelcro" cell-affinity substrates, in which CTC capture agent-coated nanostructured substrates were utilized to immobilize CTCs with remarkable efficiency. Four generations of NanoVelcro CTC assays have been developed over the past decade for a variety of clinical utilities. The 1st-gen NanoVelcro Chips, composed of a silicon nanowire substrate (SiNS) and an overlaid microfluidic chaotic mixer, were created for CTC enumeration. The 2nd-gen NanoVelcro Chips (i.e., NanoVelcro-LMD), based on polymer nanosubstrates, were developed for single-CTC isolation in conjunction with the use of the laser microdissection (LMD) technique. By grafting thermoresponsive polymer brushes onto SiNS, the 3rd-gen Thermoresponsive NanoVelcro Chips have demonstrated the capture and release of CTCs at 37 and 4 °C respectively, thereby allowing for rapid CTC purification while maintaining cell viability and molecular integrity. Fabricated with boronic acid-grafted conducting polymer-based nanomaterial on chip surface, the 4th-gen NanoVelcro Chips (Sweet chip) were able to purify CTCs with well-preserved RNA transcripts, which could be used for downstream analysis of several cancer specific RNA biomarkers. In this review article, we will summarize the development of the four generations of NanoVelcro CTC assays, and the clinical applications of each generation of devices.

Study on surface enhancement fluorescence effect of gold nanoparticle assembly structure on rough copper substrate surface

Gold nanoparticles (AuNPs) with different particle densities were assembled on mechanical polished copper substrate by simply evaporation method, and Au/Cu composite nanostructured SEF active substrate was fabricated. The morphology and optical properties of the fabricated substrates were analyzed by scanning electron microscopy (SEM) and emission spectra of Rhodamine 6G (Rh6G) fluorescent molecules. The experimental observations show that the assembled composite nanostructured substrate demonstrates strong fluorescence enhancement effect and the enhancement effect depends mainly on the configuration of the particle distribution. The study demonstrates that the plasmonic hot spots formed by AuNPs and copper surfaces play an important role in achieving fluorescence enhancement. The current work shows that the assembled substrate can be considered as a potential candidate for the preparation of sensitive bio-spectral sensing chips, and has a good reference for perfecting the SEF theoretical model.

Silver nanowires as infrared-active materials for surface-enhanced Raman scattering.

Surface-enhanced Raman scattering (SERS) is increasing in significance as a bioanalytical tool. Novel nanostructured metal substrates are required to improve performances and versatility of SERS spectroscopy. In particular, as biological tissues are relatively transparent in the infrared wavelength range, SERS-active materials suitable for infrared laser excitation are needed. Nanowires appear interesting in this respect as they show a very broad localized surface plasmon resonance band, ranging from near UV to near infrared wavelengths. The SERS activity of silver nanowires has been tested at three wavelengths and a fair enhancement at 1064 and 514 nm has been observed, whereas a very weak enhancement was present when exciting close to the nanowire extinction maximum. These experimentally measured optical properties have been contrasted with finite element method simulations. Furthermore, laser-induced optoacoustic spectroscopy measurements have shown that the extinction at 1064 nm is completely due to scattering. This result has an important implication that no heating occurs when silver nanowires are utilized as SERS-active substrates, thereby preventing possible thermal damage.

Improvement in ultra-thin hydrogenated amorphous silicon solar cells with nanocrystalline silicon oxide

Ultra-thin a-Si:H p-i-n solar cell has been proposed as advance to form three-dimensional structures on nano-structured substrates for achieving optically thick and electrically thin solar cells. However, over the years, although extensive studies have been carried out, no high efficiency was achieved yet. We found that not only the short circuit current density (Jsc) decreases, but also the open circuit voltage (Voc) and fill factor (FF) decreases with the reduction of i-layer thickness, which is opposite to the expectation. We investigated the possible root-causes for this unusual phenomenon and speculated the direct recombination of the electrons in the n-layer and the holes in the p-layer by tunneling through the thin i-layer is the main reason for the reduced Voc and FF in ultra-thin solar cells. Furthermore, the absorption in the doped layers is the most critical limitation for ultra-thin silicon solar cell efficiency because the doped layer thickness becomes comparable to the intrinsic layer. To resolve this issue, we used nanocrystalline silicon oxide (nc-SiOx:H) doped layers with a wide bandgap to reduce the parasitic absorption in the doped layers and the highly asymmetric conductivity improves the carrier collection and made a significant improvement in the cell efficiency. We achieved 8.79%, 7.65%, and 5.32% efficiencies with the i-layer thickness of only 70nm, 50nm and 20nm, respectively, which are the highest ones in ultra-thin silicon solar cells.

How Effective is Plasmonic Enhancement of Colloidal Quantum Dots for Color-Conversion Light-Emitting Devices?

Enhancing the fluorescence intensity of colloidal quantum dots (QDs) in case of color-conversion type QD light-emitting devices (LEDs) is very significant due to the large loss of QDs and their quantum yields during fabrication processes, such as patterning and spin-coating, and can therefore improve cost-effectiveness. Understanding the enhancement process is crucial for the design of metallic nanostructure substrates for enhancing the fluorescence of colloidal QDs. In this work, improved color conversion of colloidal green and red QDs coupled with aluminum (Al) and silver (Ag) nanodisk (ND) arrays designed by in-depth systematic finite-difference time domain simulations of excitation, spontaneous emission, and quantum efficiency enhancement is reported. Calculated results of the overall photoluminescence enhancement factor in the substrate of 500 × 500 µm2 size are 2.37-fold and 2.82-fold for Al ND-green QD and Ag ND-red QD structures, respectively. Experimental results are in good agreement, showing 2.26-fold and 2.66-fold enhancements for Al ND and Ag ND structures. Possible uses of plasmonics in cases such as white LED and total color conversion for possible display applications are discussed. The theoretical treatments and experiments shown in this work are a proof of principle for future studies of plasmonic enhancement of various light-emitting materials.

Highly efficient isolation and release of circulating tumor cells based on size-dependent filtration and degradable ZnO nanorods substrate in a wedge-shaped microfluidic chip.

Circulating tumor cells (CTCs) have been regarded as the major cause of metastasis, holding significant insights for tumor diagnosis and treatment. Although many efforts have been made to develop methods for CTC isolation and release in microfluidic system, it remains significant challenges to realize highly efficient isolation and gentle release of CTCs for further cellular and bio-molecular analyses. In this study, we demonstrate a novel method for CTC isolation and release using a simple wedge-shaped microfluidic chip embedding degradable znic oxide nanorods (ZnNRs) substrate. By integrating size-dependent filtration with degradable nanostructured substrate, the capture efficiencies over 87.5% were achieved for SKBR3, PC3, HepG2 and A549 cancer cells spiked in healthy blood sample with the flow rate of 100μL min-1. By dissolving ZnNRs substrate with an extremely low concentration of phosphoric acid (12.5mM), up to 85.6% of the captured SKBR3 cells were released after reverse injection with flow rate of 100μL min-1 for 15min, which exhibited around 73.6% cell viability within 1h after release to around 93.9% after re-cultured for 3days. It is conceivable that our microfluidic device has great potentials in carrying on cell-based biomedical studies and guiding individualized treatment in the future.

Development of Sphere-Polymer Brush Hierarchical Nanostructure Substrates for Fabricating Microarrays with High Performance.

In this work, a sphere-polymer brush hierarchical nanostructure-modified glass slide has been developed for fabricating high-performance microarrays. The substrate consists of a uniform 160 nm silica particle-self-assembled monolayer on a glass slide with a postcoated poly(glycidyl methacrylate) (PGMA) brush layer (termed PGMA@3D(160) substrate), which can provide three-dimensional (3D) polymer brushes containing abundant epoxy groups for directly immobilizing various biomolecules. As a typical example, the interactions of three monosaccharides (4-aminophenyl β-d-galactopyranoside, 4-aminophenyl β-d-glucopyranoside, and 4-aminophenyl α-d-mannopyranoside) with two lectins (biotinylated ricinus communis agglutinin 120 and biotinylated concanavalin A from Canavalia ensiformis) have been assessed by PGMA@3D(160) substrate-based carbohydrate microarrays. The carbohydrate microarrays show good selectivity, strong multivalent interaction, and low limit of detection (LOD) in the picomolar range without any signal amplification. Furthermore, the proposed sphere-polymer brush hierarchical nanostructure substrates can be easily extended to fabricate other types of microarrays for DNA and protein detection. PGMA@3D(160) substrate-based microarrays exhibit higher reaction efficiencies and lower LODs (by at least 1 order of magnitude) in comparison to those of two-dimensional microarrays, which are fabricated on planar epoxy substrates, making it a promising platform for bioanalytical and biomedical applications.

Modeling of the interaction between osteoblasts and biocompatible substrates as a function of adhesion strength.

A goal of current implantology research is to design devices that induce controlled, guided, and rapid healing. Nanoscale structured substrates [e.g., titania nanotubes (TNTs) or carbon nanotubes (CNTs)] dramatically improve the functions of conventional biomaterials. The present investigation evaluated the behavior of osteoblasts cells cultured on smooth and nanostructured substrates, by measuring osteoblasts specific biomarkers [alkaline phosphatase (AP) and total protein] and cells adhesion strength to substrates, followed by semi-empirical modeling to predict the experimental results. Findings were in total agreement with the current state of the art. The proliferation, as well as the AP and total protein levels were higher on the nanostructure phases (TNTs, CNTs) comparing to the smooth ones (plastic and pure titanium). Cells adhesion strength measured was found higher on the nanostructured materials. This coincided with a higher value of proteins which are directly implicated in the process of adherence. Results were accurately predicted through the Viscoelastic Hybrid Interphase Model. A gradual adherence of bone cells to implants using multilayered biomaterials that involve biodegradable polymeric films and a nanoscale modification of titanium surface is suggested to improve performance through an interphase-mediated osteointegration of orthopedic implants. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 106A: 621-628, 2018.

Engineering of nanostructured plasmonic substrates for use as SERS sensors

Plasmonic nanostructures strongly localize electric fields on their surfaces via the collective oscillations of conducting electrons under stimulation by incident light at certain wavelength. Molecules adsorbed onto such surfaces experiences a strongly enhanced electric field due to the localized surface plasmon resonance (LSPR), which amplifies the Raman scattering signal from these molecules. This phenomenon is referred to as surface enhanced Raman scattering (SERS). Further enhancements in the Raman intensity have been achieved by designing plasmonic nanostructures with a controlled size, shape, composition, and arrangement. This review paper focuses on the theory and analyses the influence of protective coating with oxide materials an isolated plasmonic metal nanostructures. Starting with a brief description of the basic principles underlying LSPR and SERS, we compare two plasmonic metals, two dielectric materials and the effect of changing individual parameters of the nanostructure on output enhanced Raman signal.

Molecular recognition and detection of Pb(II) ions in water by aminobenzo-18-crown-6 immobilised onto a nanostructured SERS substrate

In this work, we propose a new sensitive, selective and portable surface enhanced Raman spectroscopy (SERS) methodology for the rapid on site detection of Pb(II) pollution in water. The new method utilises aminobenzo-18-crown-6 (AB18C6) as a selective recognition molecule to form a spontaneous complex with Pb(II) ions. The formed AB18C6-Pb(II) complex was rapidly immobilised onto a nanostructured gold substrate via Au-N bond formation and reproducibly screened by SERS using a handheld Raman device. For the SERS measurements, a substrate was fabricated by electrochemical deposition of gold nanostructures onto a flat gold disc, creating multiple hotspots for ultrasensitive SERS measurements. The limit of quantification (LOQ) for Pb(II) ions by the SERS method was 2.20pM. The limit of detection (LOD) was 0.69pM which is five orders of magnitude lower than the maximum Pb(II) level of 72nM allowed by the US Environmental Protection Agency. The high sensitivity of the SERS substrate is attributed to the coupling between the Surface Plasmon Polariton (SPP) of its gold surface, the localised Surface Plasmon Resonance (SPR) of the gold nanostructures and the Raman radiation from the immobilised AB18C6-Pb(II) complex. The new SERS detection method was successfully applied for the selective and rapid screening of Pb(II) ion contamination in water proving its practical application for environmental analysis.