Nanostructured Titanium Dioxide Surfaces for Electrochemical Biosensing.

TiO2 electrochemical biosensors represent an option for biomolecules recognition associated with diseases, food or environmental contaminants, drug interactions and related topics. The relevance of TiO2 biosensors is due to the high selectivity and sensitivity that can be achieved. The development of electrochemical biosensors based on nanostructured TiO2 surfaces requires knowing the signal extracted from them and its relationship with the properties of the transducer, such as the crystalline phase, the roughness and the morphology of the TiO2 nanostructures. Using relevant literature published in the last decade, an overview of TiO2 based biosensors is here provided. First, the principal fabrication methods of nanostructured TiO2 surfaces are presented and their properties are briefly described. Secondly, the different detection techniques and representative examples of their applications are provided. Finally, the functionalization strategies with biomolecules are discussed. This work could contribute as a reference for the design of electrochemical biosensors based on nanostructured TiO2 surfaces, considering the detection technique and the experimental electrochemical conditions needed for a specific analyte.

Synergic antibacterial coatings combining titanium nanocolumns and tellurium nanorods.

Nanocolumnar titanium coatings have been fabricated in two sputtering systems with very different characteristics (a laboratory setup and semi-industrial equipment), thus possessing different morphologies (150 nm long columns tilted 20° from the normal and 300 nm long ones tilted 40°, respectively). These coatings exhibit similar antibacterial properties against Gram positive (Staphylococcus aureus) and Gram negative (Escherichia coli) bacteria. When a synergic route is followed and these coatings are functionalized with tellurium (Te) nanorods, the antibacterial properties are enhanced, especially for the long nanocolumns case. The biocompatibility is preserved in all the nanostructured coatings.

Parallel collective resonances in arrays of gold nanorods.

In this work we discuss the excitation of parallel collective resonances in arrays of gold nanoparticles. Parallel collective resonances result from the coupling of the nanoparticles localized surface plasmons with diffraction orders traveling in the direction parallel to the polarization vector. While they provide field enhancement and delocalization as the standard collective resonances, our results suggest that parallel resonances could exhibit greater tolerance to index asymmetry in the environment surrounding the arrays. The near- and far-field properties of these resonances are analyzed, both experimentally and numerically.

Gold Nanocolumnar Templates for Effective Chemical Sensing by Surface-Enhanced Raman Scattering.

Herein, we investigate the chemical sensing by surface-enhanced Raman scattering regarding two templates of gold nanocolumns (vertical and tilted) manufactured by glancing angle deposition with magnetron sputtering. We selected this fabrication technique due to its advantages in terms of low-cost production and ease of implementation. These gold nanocolumnar structures allow producing a high density of strongly confined electric field spots within the nanogaps between the neighboring nanocolumns. Thiophenol molecules were used as model analytes since they have the principal property to adsorb well on gold surfaces. Regarding chemical sensing, the vertical (tilted) nanocolumnar templates showed a detection threshold limit of 10 nM (20 nM), an enhancement factor of 9.8 × 108 (4.8 × 108), and a high quality of adsorption with an adsorption constant Kads of 2.0 × 106 M-1 (1.8 × 106 M-1) for thiophenol molecules.

Large-Area Nanopillar Arrays by Glancing Angle Deposition with Tailored Magnetic Properties.

Ferromagnetic films down to thicknesses of tens of nanometers and composed by polycrystalline Fe and Fe2O3 nanopillars are grown in large areas by glancing angle deposition with magnetron sputtering (MS-GLAD). The morphological features of these films strongly depend on the growth conditions. Vertical or tilted nanopillars have been fabricated depending on whether the substrate is kept rotating azimuthally during deposition or not, respectively. The magnetic properties of these nanopillars films, such as hysteresis loops squareness, adjustable switching fields, magnetic anisotropy and coercivity, can be tuned with the specific morphology. In particular, the growth performed through a collimator mask mounted onto a not rotating azimuthally substrate produces almost isolated well-defined tilted nanopillars that exhibit a magnetic hardening. The first-order reversal curves diagrams and micromagnetic simulations revealed that a growth-induced uniaxial anisotropy, associated with an anisotropic surface morphology produced by the glancing angle deposition in the direction perpendicular to the atomic flux, plays an important role in the observed magnetic signatures. These results demonstrate the potential of the MS-GLAD method to fabricate nanostructured films in large area with tailored structural and magnetic properties for technological applications.

Effects of nanostructuration on the electrochemical performance of metallic bioelectrodes.

The use of metallic nanostructures in the fabrication of bioelectrodes (e.g., neural implants) is gaining attention nowadays. Nanostructures provide increased surface area that might benefit the performance of bioelectrodes. However, there is a need for comprehensive studies that assess electrochemical performance of nanostructured surfaces in physiological and relevant working conditions. Here, we introduce a versatile scalable fabrication method based on magnetron sputtering to develop analogous metallic nanocolumnar structures (NCs) and thin films (TFs) from Ti, Au, and Pt. We show that NCs contribute significantly to reduce the impedance of metallic surfaces. Charge storage capacity of Pt NCs is remarkably higher than that of Pt TFs and that of the other metals in both morphologies. Circuit simulations of the electrode/electrolyte interface show that the signal delivered in voltage-controlled systems is less filtered when nanocolumns are used. In a current-controlled system, simulation shows that NCs provide safer stimulation conditions compared to TFs. We have assessed the durability of NCs and TFs for potential use in vivo by reactive accelerated aging test, mimicking one-year in vivo implantation. Although each metal/morphology reveals a unique response to aging, NCs show overall more stable electrochemical properties compared to TFs in spite of their porous structure.

Pepper-Mediated Green Synthesis of Selenium and Tellurium Nanoparticles with Antibacterial and Anticancer Potential.

The production of nanoparticles for biomedical applications (namely with antimicrobial and anticancer properties) has been significantly hampered using traditional physicochemical approaches, which often produce nanostructures with poor biocompatibility properties requiring post-synthesis functionalization to implement features that such biomedical applications require. As an alternative, green nanotechnology and the synthesis of environmentally friendly nanomaterials have been gaining attention over the last few decades, using living organisms or biomolecules derived from them, as the main raw materials to produce cost-effective, environmentally friendly, and ready-to-be-used nanomaterials. In this article and building upon previous knowledge, we have designed and implemented the synthesis of selenium and tellurium nanoparticles using extracts from fresh jalapeño and habanero peppers. After characterization, in this study, the nanoparticles were tested for both their antimicrobial and anticancer features against isolates of antibiotic-resistant bacterial strains and skin cancer cell lines, respectively. The nanosystems produced nanoparticles via a fast, eco-friendly, and cost-effective method showing different antimicrobial profiles between elements. While selenium nanoparticles lacked an antimicrobial effect at the concentrations tested, those made of tellurium produced a significant antibacterial effect even at the lowest concentration tested. These effects were correlated when the nanoparticles were tested for their cytocompatibility and anticancer properties. While selenium nanoparticles were biocompatible and had a dose-dependent anticancer effect, tellurium-based nanoparticles lacked such biocompatibility while exerting a powerful anti-cancer effect. Further, this study demonstrated a suitable mechanism of action for killing bacteria and cancer cells involving reactive oxygen species (ROS) generation. In summary, this study introduces a new green nanomedicine synthesis approach to create novel selenium and tellurium nanoparticles with attractive properties for numerous biomedical applications.

A Magnetic Force Microscopy Study of Patterned T-Shaped Structures.

The study of patterned magnetic elements that can sustain more than one bit of the information is an important research line for developing new routes in magnetic storage and magnetic logic devices. Previous Monte Carlo studies of T-shaped magnetic nanostructures revealed the equilibrium and evolution of magnetic states that could be found as a result of the strong configurational anisotropy of these systems. In this work, for the first time, such behavior of T-shaped magnetic nanostructures is experimentally studied. In particular, T-shaped Co nanostructures have been produced by electron beam lithography using a single step lift-off process over Si substrates. The existence of four magnetic stable states has been proven by Magnetic Force Microscopy (MFM) and the analysis was complemented by Micromagnetic Simulations. The results confirmed that even for what can be considered large structures, with µm sizes, such four stable magnetic states can be achieved, and therefore two magnetic bits of information can be stored. We also addressed how to write and read those bits.

Green synthesis and characterization of gold-based anisotropic nanostructures using bimetallic nanoparticles as seeds.

Nanostructured noble metals are of great interest because of their tunable optical and electronic properties. However, the green synthesis of anisotropic nanostructures with a defined geometry by the systematic nanoassembly of particles into specific shape, size, and crystallographic facets still faces major challenges. The present work aimed to establish an environmentally friendly methodology for synthesizing gold-based anisotropic nanostructures using starch-capped bimetallic silver/gold nanoparticles as seeds and hydrogen peroxide as a reducing agent.

Green synthesis of starch-capped Cu2O nanocubes and their application in the direct electrochemical detection of glucose.

Glucose determination is an essential procedure in different fields, used in clinical analysis for the prevention and monitoring of diabetes. In this work, modified carbon paste electrodes with Cu2O nanocubes (Cu2O NCs) were developed to test electrochemical glucose detection. The synthesis of the Cu2O NCs was achieved by a green method using starch as the capping agent, obtaining cubic-like morphologies and particle sizes from 227 to 123 nm with increasing amounts of the capping agent, as corroborated by electron microscopy analysis. Their crystalline structure and purity were determined by X-ray diffraction. The capability of starch as a capping agent was verified by Fourier-transform infrared spectroscopy, in which the presence of functional groups of this biopolymer in the Cu2O NCs were identified. The electrochemical response to glucose oxidation was determined by cyclic voltammetry, obtaining a linear response of the electrical current as a function of glucose concentration in the range 100-700 µM, with sensitivities from 85.6 to 238.8 µA mM-1 cm-2, depending on the amount of starch used in the synthesis of the Cu2O NCs.

Aloe Vera-Mediated Te Nanostructures: Highly Potent Antibacterial Agents and Moderated Anticancer Effects.

Cancer and antimicrobial resistance to antibiotics are two of the most worrying healthcare concerns that humanity is facing nowadays. Some of the most promising solutions for these healthcare problems may come from nanomedicine. While the traditional synthesis of nanomaterials is often accompanied by drawbacks such as high cost or the production of toxic by-products, green nanotechnology has been presented as a suitable solution to overcome such challenges. In this work, an approach for the synthesis of tellurium (Te) nanostructures in aqueous media has been developed using aloe vera (AV) extracts as a unique reducing and capping agent. Te-based nanoparticles (AV-TeNPs), with sizes between 20 and 60 nm, were characterized in terms of physicochemical properties and tested for potential biomedical applications. A significant decay in bacterial growth after 24 h was achieved for both Methicillin-resistant Staphylococcus aureus and multidrug-resistant Escherichia coli at a relative low concentration of 5 µg/mL, while there was no cytotoxicity towards human dermal fibroblasts after 3 days of treatment. AV-TeNPs also showed anticancer properties up to 72 h within a range of concentrations between 5 and 100 µg/mL. Consequently, here, we present a novel and green approach to produce Te-based nanostructures with potential biomedical applications, especially for antibacterial and anticancer applications.

Green nanotechnology-based drug delivery systems for osteogenic disorders.

Introduction: Current treatments for osteogenic disorders are often successful, however they are not free of drawbacks, such as toxicity or side effects. Nanotechnology offers a platform for drug delivery in the treatment of bone disorders, which can overcome such limitations. Nevertheless, traditional synthesis of nanomaterials presents environmental and health concerns due to its production of toxic by-products, the need for extreme and harsh raw materials, and their lack of biocompatibility over time.Areas covered: This review article contains an overview of the current status of treating osteogenic disorders employing green nanotechnological approaches, showing some of the latest advances in the application of green nanomaterials, as drug delivery carriers, for the effective treatment of osteogenic disorders.Expert opinion: Green nanotechnology, as a potential solution, is understood as the use of living organisms, biomolecules and environmentally friendly processes for the production of nanomaterials. Nanomaterials derived from bacterial cultures or biomolecules isolated from living organisms, such as carbohydrates, proteins, and nucleic acids, have been proven to be effective composites. These nanomaterials introduce enhancements in the treatment and prevention of osteogenic disorders, compared to physiochemically-synthesized nanostructures, specifically in terms of their improved cell attachment and proliferation, as well as their ability to prevent bacterial adhesion.

TiO2 Nanocolumn Arrays for More Efficient and Stable Perovskite Solar Cells.

Organic-inorganic hybrid perovskite solar cells have attracted much attention due to their high power conversion efficiency (>25%) and low-cost fabrication. Yet, improvements are still needed for more stable and higher-performing solar cells. In this work, a series of TiO2 nanocolumn photonic structures have been intentionally fabricated on half of the compact TiO2-coated fluorine-doped tin oxide substrate by glancing angle deposition with magnetron sputtering, a method particularly suitable for industrial applications due to its high reliability and reduced cost when coating large areas. These vertically aligned nanocolumn arrays were then applied as the electron transport layer into triple-cation lead halide perovskite solar cells based on Cs0.05(FA0.83MA0.17)0.95Pb(I0.83Br0.17)3. By comparison to solar cells built onto the same substrate without nanocolumns, the use of TiO2 nanocolumns can significantly enhance the power conversion efficiency of the perovskite solar cells by 7% and prolong their shelf life. Here, detailed characterizations on the morphology and the spectroscopic aspects of the nanocolumns, their near-field and far-field optical properties, solar cells characteristics, as well as the charge transport properties provide mechanistic insights on how one-dimensional TiO2 nanocolumns affect the performance of perovskite halide solar cells in terms of charge transport, light harvesting, and stability, knowledge necessary for the future design of higher-performing and more stable perovskite solar cells.

Comparison of cytocompatibility and anticancer properties of traditional and green chemistry-synthesized tellurium nanowires.

BACKGROUND: Traditional physicochemical approaches for the synthesis of compounds, drugs, and nanostructures developed as potential solutions for antimicrobial resistance or against cancer treatment are, for the most part, facile and straightforward. Nevertheless, these approaches have several limitations, such as the use of toxic chemicals and production of toxic by-products with limited biocompatibility. Therefore, new methods are needed to address these limitations, and green chemistry offers a suitable and novel answer, with the safe and environmentally friendly design, manufacturing, and use of minimally toxic chemicals. Green chemistry approaches are especially useful for the generation of metallic nanoparticles or nanometric structures that can effectively and efficiently address health care concerns. OBJECTIVE: Here, tellurium (Te) nanowires were synthesized using a novel green chemistry approach, and their structures and cytocompatibility were evaluated. METHOD: An easy and straightforward hydrothermal method was employed, and the Te nanowires were characterized using transmission electron microscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, Fourier-transform infrared spectroscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, and optical microscopy for morphology, size, and chemistry. Cytotoxicity tests were performed with human dermal fibroblasts and human melanoma cells (to assess anticancer properties). The results showed that a treatment with Te nanowires at concentrations between 5 and 100 µg/mL improved the proliferation of healthy cells and decreased cancerous cell growth over a 5-day period. Most importantly, the green chemistry -synthesized Te nanowires outperformed those produced by traditional synthetic chemical methods. CONCLUSION: This study suggests that green chemistry approaches for producing Te nanostructures may not only reduce adverse environmental effects resulting from traditional synthetic chemistry methods, but also be more effective in numerous health care applications.

On the Large Near-Field Enhancement on Nanocolumnar Gold Substrates.

One of the most important and distinctive features of plasmonic nanostructures is their ability to confine large electromagnetic fields on nanometric volumes; i.e., the so-called hot spots. The generation, control and characterization of the hot spots are fundamental for several applications, like surface-enhanced spectroscopies. In this work, we characterize the near-field distribution and enhancement of nanostructured gold thin films fabricated by glancing angle deposition magnetron sputtering. These films are composed of columnar nanostructures with high roughness and high density of inter-columnar gaps, where the electromagnetic radiation can be confined, generating hot spots. As expected, the hot spots are localized in the gaps between adjacent nanocolumns and we use scattering-type scanning near-field optical microscopy to image their distribution over the surface of the samples. The experimental results are compared with finite-difference time-domain simulations, finding an excellent agreement between them. The spectral dependence of the field-enhancement is also studied with the simulations, together with surface-enhanced Raman spectroscopy at different excitation wavelengths in the visible-NIR range, proving a broad-band response of the substrates. These findings may result in interesting applications in the field of surface-enhanced optical spectroscopies or sensing.

Citric Juice-mediated Synthesis of Tellurium Nanoparticles with Antimicrobial and Anticancer Properties.

Bacterial infections and cancer are two of the most significant concerns that the current healthcare system should tackle nowadays. Green nanotechnology is presented as a feasible solution that is able to produce materials with significant anticancer and antibacterial activity, while overcoming the main limitations of traditional synthesis. In the present work, orange, lemon and lime extracts were used as both reducing and capping agents for the green synthesis of tellurium nanoparticles (TeNPs) using a microwave-assisted reaction. TeNPs showed a uniform size distribution, and rod- and cubic-shapes, and were extensively characterized in terms of morphology, structure and composition using TEM, SEM, XPS, XRD, FTIR and EDX analysis. TeNPs showed an important antibacterial activity against both Gram-negative and -positive bacteria in a range concentrations from 5 to 50 µg/mL over a 24-hour time period. Besides, nanoparticles showed anticancer effect towards human melanoma cells over 48 hours at concentrations up to 50 µg/mL. Moreover, the Te nanostructures showed no significant cytotoxic effect towards human dermal fibroblast at concentrations up to 50 µg/mL. Therefore, we present an environmentally-friendly and cost-effective synthesis of TeNPs using only fruit juices and showing enhanced and desirable biomedical properties towards both infectious diseases and cancer.

Localized surface plasmon resonance effects on the magneto-optical activity of continuous Au/Co/Au trilayers.

We study how the magneto-optical activity in polar configuration of continuous Au/Co/Au trilayers is affected by the excitation of localized plasmon resonances of an array of Au nanodiscs fabricated on top of them over a dielectric SiO(2) spacer. We show that the effect of the nanodiscs array is twofold. First, it optimizes the absorption of light at specific photon energies corresponding to the localized surface plasmon excitation of the array, modifying the reflectivity of the system (we define this effect as the purely optical contribution). Second, upon localized plasmon resonance excitation, the electromagnetic field in the whole system is redistributed, and an enhanced magneto-optical activity occurs at those energies where the electromagnetic field in the magnetic layer is increased (this effect is identified as the purely magneto-optical contribution of the nanodiscs array).

Magnetic properties of Fe3O4 antidot arrays synthesized by AFIR: atomic layer deposition, focused ion beam and thermal reduction.

Magnetic films of magnetite (Fe3O4) with controlled defects, so-called antidot arrays, were synthesized by a new technique called AFIR. AFIR consists of the deposition of a thin film by atomic layer deposition, the generation of square and hexagonal arrays of holes using focused ion beam milling, and the subsequent thermal reduction of the antidot arrays. Magnetic characterizations were carried out by magneto-optic Kerr effect measurements, showing the enhancement of the coercivity for the antidot arrays. AFIR opens a new route to manufacture ordered antidot arrays of magnetic oxides with variable lattice parameters.

Fabrication of black-gold coatings by glancing angle deposition with sputtering.

The fabrication of black-gold coatings using sputtering is reported here. Glancing angle deposition with a rotating substrate is needed to obtain vertical nanostructures. Enhanced light absorption is obtained in the samples prepared in the ballistic regime with high tilt angles. Under these conditions the diameter distribution of the nanostructures is centered at about 60 nm and the standard deviation is large enough to obtain black-metal behavior in the visible range.

Nanometer Scale Hard/Soft Bilayer Magnetic Antidots.

The effect of arrays of nanometer scale pores on the magnetic properties of thin films has been analyzed. Particularly, we investigated the influence of the out-of-plane magnetization component created by the nanopores on the in-plane magnetic behavior of patterned hard/soft magnetic thin films in antidot morphology. Its influence on the coupling in Co/Py bilayers of few tens of nanometer thick is compared for disordered and ordered antidots of 35-nm diameter. The combination of magneto-optical Kerr effect (MOKE) and first-order reversal curve (FORC) technique allows probing the effects of the induced perpendicular magnetization component on the bilayer magnetic behavior, while magnetic force microscopy (MFM) is used to image it. We found that ordered antidots yield a stronger out-of-plane component than disordered ones, influencing in a similar manner the hard layer global in-plane magnetic behavior if with a thin or without soft layer. However, its influence changes with a thicker soft layer, which may be an indication of a weaker coupling.