Influence of the Micro-Nanostructuring of Titanium Dioxide Films on the Photocatalytic Degradation of Formic Acid under UV Illumination.

Surface micro-nanostructuring can provide new functionalities and properties to coatings. For example, it can improve the absorption efficiency, hydrophobicity and/or tribology properties. In this context, we studied the influence of micro-nanostructuring on the photocatalytic efficiency of sol-gel TiO2 coatings during formic acid degradation under UV illumination. The micro-nanostructuring was performed using the UV illumination of microspheres deposited on a photopatternable sol-gel layer, leading to a hexagonal arrangement of micropillars after development. The structures and coatings were characterized using Raman spectroscopy, ellipsometry, atomic force microscopy and scanning electron microscopy. When the sol-gel TiO2 films were unstructured and untreated at 500 °C, their effect on formic acid's degradation under UV light was negligible. However, when the films were annealed at 500 °C, they crystallized in the anatase phase and affected the degradation of formic acid under UV light, also depending on the thickness of the layer. Finally, we demonstrated that surface micro-nanostructuring in the form of nanopillars can significantly increase the photocatalytic efficiency of a coating during the degradation of formic acid under UV light.

Anti-Counterfeiting White Light Printed Image Multiplexing by Fast Nanosecond Laser Processing.

Passive plasmonic metasurfaces enable image multiplexing by displaying different images when altering the conditions of observation. Under white light, three-image multiplexing with polarization-selective switching has been recently demonstrated using femtosecond-laser-processed random plasmonic metasurfaces. Here, the implementation of image multiplexing is extended, thanks to a color-search algorithm, to various observation modes compatible with naked-eye observation under incoherent white light and to four-image multiplexing under polarized light. The laser-processed random plasmonic metasurfaces enabling image multiplexing exhibit self-organized patterns that can diffract light or induce dichroism through hybridization between the localized surface plasmon resonance of metallic nanoparticles and a lattice resonance. Improved spatial resolution makes the image quality compatible with commercial use in secured documents as well as the processing time and cost thanks to the use of a nanosecond laser. This high-speed and flexible laser process, based on energy-efficient nanoparticle reshaping and self-organization, produces centimeter-scale customized tamper-proof images at low cost, which can serve as overt security features.

Impact of γ-rays Irradiation on Hybrid TiO2-SiO2 Sol-Gel Films Doped with RHODAMINE 6G.

In the present paper, we investigate how the optical and structural properties, in particular the observed photoluminescence (PL) of photocurable and organic-inorganic TiO2-SiO2 sol-gel films doped with Rhodamine 6G (R6G) are affected by γ-rays. For this, four luminescent films, firstly polymerized with UV photons (365 nm), were submitted to different accumulated doses of 50 kGy, 200 kGy, 500 kGy and 1 MGy while one sample was kept as a reference and unirradiated. The PL, recorded under excitations at 365 nm, 442 nm and 488 nm clearly evidences that a strong signal peaking at 564 nm is still largely present in the γ-irradiated samples. In addition, M-lines and Fourier-transform infrared (FTIR) spectroscopies are used to quantify the radiation induced refractive index variation and the chemical changes, respectively. Results show that a refractive index decrease of 7 × 10-3 at 633 nm is achieved at a 1 MGy accumulated dose while a photo-induced polymerization occurs, related to the consumption of CH=C, Si-OH and Si-O-CH3 groups to form Ti-O and Si-O bonds. All these results confirm that the host matrix (TiO2-SiO2) and R6G fluorophores successfully withstand the hard γ-ray exposure, opening the way to the use of this material for sensing applications in radiation-rich environments.

Comparison between the UV and X-ray Photosensitivities of Hybrid TiO2-SiO2 Thin Layers.

The photo-induced effects on sol-gel-based organo TiO2-SiO2 thin layers deposited by the dip-coating technique have been investigated using two very different light sources: A light-emitting diode (LED) emitting in the UV (at 365 nm, 3.4 eV) and an X-ray tube producing 40 keV mean-energy photons. The impact of adding a photo-initiator (2,2-dimethoxy-2-phenylacetophenone-DMPA) on the sol-gel photosensitivity is characterized namely in terms of the photo-induced refractive index measured through M-line spectroscopy. Results show that both silica-titania sol-gel films with or without the photo-initiator are photosensitive to both photon sources. The induced refractive index values reveal several features where slightly higher refractive indexes are obtained for the sol-gel containing the photo-initiator. UV and X-ray-induced polymerization degrees are discussed using Fourier-transform infrared (FTIR) spectroscopy where the densification of hybrid TiO2-SiO2 layers is related to the consumption of the CH=C groups and to the decomposition of Si-OH and Si-O-CH3 bonds. X-rays are more efficient at densifying the TiO2-SiO2 inorganic and organic network with respect to the UV photons. Hard X-ray photolithography, where no cracks or damages are observed after intense exposition, can be a promising technique to design submicronic-structure patterns on TiO2-SiO2 thin layers for the building of optical sensors.

Periodic TiO2 Nanostructures with Improved Aspect and Line/Space Ratio Realized by Colloidal Photolithography Technique.

This paper presents substantial improvements of the colloidal photolithography technique (also called microsphere lithography) with the goal of better controlling the geometry of the fabricated nano-scale structures-in this case, hexagonally arranged nanopillars-printed in a layer of directly photopatternable sol-gel TiO2. Firstly, to increase the achievable structure height the photosensitive layer underneath the microspheres is deposited on a reflective layer instead of the usual transparent substrate. Secondly, an increased width of the pillars is achieved by tilting the incident wave and using multiple exposures or substrate rotation, additionally allowing to better control the shape of the pillar's cross section. The theoretical analysis is carried out by rigorous modelling of the photonics nanojet underneath the microspheres and by optimizing the experimental conditions. Aspect ratios (structure height/lateral structure size) greater than 2 are predicted and demonstrated experimentally for structure dimensions in the sub micrometer range, as well as line/space ratios (lateral pillar size/distance between pillars) greater than 1. These nanostructures could lead for example to materials exhibiting efficient light trapping in the visible and near-infrared range, as well as improved hydrophobic or photocatalytic properties for numerous applications in environmental and photovoltaic systems.

Microstructuring of Mesoporous Titania Films Loaded with Silver Salts to Enhance the Photocatalytic Degradation of Methyl Blue under Visible Light.

The microstructuring of the distribution of silver nanoparticles (NPs) in mesoporous titania films loaded with silver salts, using two-beam interference lithography leading to 1 Dimension (1D) grating, induces variations in the photocatalytic efficiency. The influence of the structuration was tested on the degradation of methyl blue (MB) under ultraviolet (UV) and visible illumination, giving rise to a significant improvement of the photocatalytic efficiency. The periodic distribution of the NPs was characterized by transmission electron microscopy (TEM), high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) and scanning electron microscopy (SEM).

Three-Dimensional Self-Organization in Nanocomposite Layered Systems by Ultrafast Laser Pulses.

Controlling plasmonic systems with nanometer resolution in transparent films and their colors over large nonplanar areas is a key issue for spreading their use in various industrial fields. Using light to direct self-organization mechanisms provides high-speed and flexible processes to meet this challenge. Here, we describe a route for the laser-induced self-organization of metallic nanostructures in 3D. Going beyond the production of planar nanopatterns, we demonstrate that ultrafast laser-induced excitation combined with nonlinear feedback mechanisms in a nanocomposite thin film can lead to 3D self-organized nanostructured films. The process, which can be extended to complex layered composite systems, produces highly uniform large-area nanopatterns. We show that 3D self-organization originates from the simultaneous excitation of independent optical modes at different depths in the film and is activated by the plasmon-induced charge separation and thermally induced NP growth mechanisms. This laser color marking technique enables multiplexed optical image encoding and the generated nanostructured Ag NPs:TiO2 films offer great promise for applications in solar energy harvesting, photocatalysis, or photochromic devices.

Aflatoxin B1 Detection Using a Highly-Sensitive Molecularly-Imprinted Electrochemical Sensor Based on an Electropolymerized Metal Organic Framework.

A sensitive electrochemical molecularly-imprinted sensor was developed for the detection of aflatoxin B1 (AFB1), by electropolymerization of p-aminothiophenol-functionalized gold nanoparticles in the presence of AFB1 as a template molecule. The extraction of the template leads to the formation of cavities that are able to specifically recognize and bind AFB1 through π-π interactions between AFB1 molecules and aniline moities. The performance of the developed sensor for the detection of AFB1 was investigated by linear sweep voltammetry using a hexacyanoferrate/hexacyanoferrite solution as a redox probe, the electron transfer rate increasing when the concentration of AFB1 increases, due to a p-doping effect. The molecularly-imprinted sensor exhibits a broad linear range, between 3.2 fM and 3.2 µM, and a quantification limit of 3 fM. Compared to the non-imprinted sensor, the imprinting factor was found to be 10. Selectivity studies were also performed towards the binding of other aflatoxins and ochratoxin A, proving good selectivity.

Anticancer drug detection using a highly sensitive molecularly imprinted electrochemical sensor based on an electropolymerized microporous metal organic framework.

A simple and highly sensitive approach for the detection of the anti-neoplastic drug gemcitabine is presented, based on a one-step electropolymerized molecularly imprinted microporous-metal-organic-framework. The sensitive layer was prepared by electropolymerization of the aniline moieties of p-aminothiophenol- gold nanoparticles on the surface of gold electrodes tethered with p-aminothiophenol, in the presence of gemcitabine as a template molecule. Experimental parameters that control the performance of the sensor were investigated and optimized. Under optimal conditions a calibration curve was obtained in the linear range from 3.8 fM to 38 nM with a limit of detection of 3 fM. The obtained imprinted sensor has the advantages of easy manufacture, high sensitivity and selectivity and good reproducibility. Furthermore the feasibility of the proposed technique has been investigated on spiked serum samples and infusion solution containing gemcitabine.

Enhanced response of a proteinase K-based conductometric biosensor using nanoparticles.

Proteinases are involved in a multitude of important physiological processes, such as protein metabolism. For this reason, a conductometric enzyme biosensor based on proteinase K was developed using two types of nanoparticles (gold and magnetic). The enzyme was directly adsorbed on negatively charged nanoparticles and then deposited and cross-linked on a planar interdigitated electrode (IDE). The biosensor was characterized with bovine serum albumin (BSA) as a standard protein. Higher sensitivity was obtained using gold nanoparticles. The linear range for BSA determination was then from 0.5 to 10 mg/L with a maximum response of 154 µs. These results are greater than that found without any nanoparticles (maximum response of 10 µs). The limit of detection (LOD) was 0.3 mg/L. An inter-sensor reproducibility of 3.5% was obtained.

Laser-induced periodic alignment of Ag nanoparticles in soda-lime glass.

One-, two- or three-dimensional arrays of closely spaced silver nanoparticles may lead to new optical properties, due to short or long range coupling between their resonant surface plasmons, so that the spatially controlled growth of silver nanoparticles provides an efficient way to tune their optical properties. Towards this way, we present here the periodic pattern of a glass surface with silver nanoparticles by continuous ultraviolet laser exposure. The formation of the 160 nm period pattern is well described by an interference-based model which agrees with the experimental conclusions, mainly obtained by various forms of microscopy. Statistical approach based on the autocorrelation function gives quantitative description about the quality of the order in the periodic structure and about the nanoparticles averaged diameter (80 nm). We also present the optical extinction spectrum of the Laser Induced Periodic Surface Structure (LIPSS)-containing area of the glass, which unusually shows several bands in the visible range. The period of 160 nm of the periodic structure is short enough to allow coupling between nanoparticles, which makes it a possible candidate for plasmon-based optical applications.

Comparative study of conductometric glucose biosensor based on gold and on magnetic nanoparticles.

The aim of this study was to show the feasibility and the performances of nanoparticle biosensing. A glucose conductometric biosensor was developed using two types of nanoparticles (gold and magnetic), glucose oxidase (GOD) being adsorbed on PAH (poly(allylamine hydrochloride)) modified nanoparticles, deposited on a planar interdigitated electrode (IDEs). The best sensitivities for glucose detection were obtained with magnetic nanoparticles (70 µM/mM and 3 µM of detection limit) compared to 45 µM/mM and 9 µM with gold nanoparticles and 30 µM/mM and 50 µM with GOD directly cross-linked on IDEs. When stored in phosphate buffer (20 mM, pH 7.3) at 4 °C, the biosensor showed good stability for more than 12 days.

SBA-15 mesoporous silica coated with macrocyclic calix[4]arene derivatives: solid extraction phases for heavy transition metal ions.

A layer of macrocyclic calix[4]arene derivatives has been grafted on the internal surface of the mesochannels of the ordered mesoporous SBA-15 to develop highly efficient trap for heavy transition metal (HTM) ions. To ensure the successful anchoring of calix[4]arene derivatives on the surface of SBA-15, two different types of calix[4]arene derivatives, one with one trimethoxysilane functional group and another with two trimethoxysilane functional groups have been explored. XRD, N(2) adsorption and TEM results provide strong evidence that the mesoporous structure of the supporting materials retain their long range ordering throughout the grafting process. Solid-state NMR, TG and FT-IR spectroscopy indicate that both types of calix[4]arene derivatives can be well-anchored on the surface of the wall of SBA-15. Calix[4]arene derivative with only one trimethoxysilane functional group showed high grafting efficiency compared to that with two trimethoxysilane functional groups due to the intramolecular and intermolecular polycondensation between two trimethoxysilane functional groups. The HTM ions extraction capacity in aqueous solution of macrocycle functionalized SBA-15 nanohybrides for a series of HTM ions has been studied. The obtained materials demonstrated very high HTM ions extraction capacity up to 96% for Pb(2+) in aqueous solution.

Characterization of a self-assembled monolayer based on a calix[4]crown-5 derivate: fabrication of a chemical sensor sensitive to calcium.

The synthesis and self-assembled monolayer (SAM) formation of a calix[4]crown-5 derivative are reported. Several techniques, including electrochemistry, atomic force microscopy (AFM), Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and contact angle measurements have been applied to characterise the monolayer film designed for chemical sensor applications. The recognition properties of this SAM for metal cations has been investigated using impedance spectroscopy (IS) showing an electrochemical response proportional to calcium ion concentration in the range from 10(-7) M to 10(-2) M. This response is related to microscopic changes at the gold surface induced by selective binding by the immobilised calixarene.

A calixarene-based copper-centered redox switch as a data storage prototype.

A new copper redox molecular switch based on a calixarene possessing both imidazole- and quinoline-like fragments displays, through an exchange of ligands triggered by an electrochemical input, unexpected long-lasting stability of both the redox forms, as well as fast reversible cycling.

Gadolinium chelate coated gold nanoparticles as contrast agents for both X-ray computed tomography and magnetic resonance imaging.

Functionalized gold nanoparticles were applied as contrast agents for both in vivo X-ray and magnetic resonance imaging. These particles were obtained by encapsulating gold cores within a multilayered organic shell which is composed of gadolinium chelates bound to each other through disulfide bonds. The contrast enhancement in MRI stems from the presence of gadolinium ions which are entrapped in the organic shell, whereas the gold core provides a strong X-ray absorption. This study revealed that these particles suited for dual modality imaging freely circulate in the blood vessels without undesirable accumulation in the lungs, spleen, and liver.