A novel and stretchable carbon-nanotube/Ni@TiO2:W photocatalytic composite for the complete removal of diclofenac drug from the drinking water.

We present the structural, morphological and photocatalytic properties of stretchable composites made with carbon nanotubes (CNTs), silicon rubber and Ni@TiO2:W nanoparticles (TiWNi NPs) with average size of 37 ± 2 nm. Microscopy images showed that the TiWNi NPs decorated the surface of the CNT fibers, which are oriented in a preferential direction. TiWNi NPs presented a mixture of anatase/rutile phases with cubic structure. The performance of the TiWNi powders and stretchable composites was evaluated for the photocatalytic degradation of diclofenac (DCF) anti-inflammatory drug under ultraviolet-visible light. The results revealed that the maximum DCF degradation percentages were 34.6%, 91.9%, 97.1%, 98.5% and 100% for the CNT composite (stretched at 0%), TiWNi powders, CNT + TiWNi (stretched at 0%), CNT + TiWNi (stretched at 50%) and CNT + TiWNi (stretched at 100%), respectively. Thus, stretching the CNT + TiWNi composites was a good strategy to enhance the DCF degradation percentage from 97.1% to 100%, since stretching created additional defects (oxygen vacancies) that acted as electron sink, delaying the electron-hole recombination, and favors the DCF degradation. Raman/absorbance measurements confirmed the presence of such defects. Moreover, the reactive oxygen species (ROS) were determined by the scavenger's experiments and found that the main ROS were the ·OH and O2- radicals, which attacked the DCF molecules, causing their degradation. The results of this investigation confirmed that the stretchable CNT/TiWNi-based composites are a viable alternative to remove pharmaceutical contaminants from water and can be manually separated from the decontaminated water, which is unviable using photocatalytic powders.

A sustainable composite of rice-paper/BaMoO4 nanoparticles for the photocatalytic elimination of the recalcitrant 2,6-dichlorobenzamide (BAM) pesticide in drinking water and its mechanisms of degradation.

This research reports the use of biodegradable and flexible composites for the removal of the 2,6-dichlorobenzamide (BAM) pesticide from drinking water. Rice paper (a biodegradable substrate) and Ag/BaMoO4 (MOBA) nanoparticles were employed to fabricate these composites. The SEM images showed that the MOBA nanoparticles with sizes of 300-800 nm decorated the surface of the biodegradable substrate and formed porous agglomerates, which have sizes of 1-3 µm. The MOBA powders were dispersed in drinking water polluted with BAM and were exposed to 4 h of UV-VIS irradiation, producing a maximum degradation of 82% for the BAM. Moreover, the flexible and biodegradable rice/MOBA composite produced a maximum removal percentage of 95% for the BAM. Also, we studied the effect of pH of the initial solution utilizing both powders and composites. From here, we found that a pH of 10 leads to a complete degradation of BAM after 4h, while a pH of 3 degraded only 37-47% of BAM for the same reaction time. According to the scavenger experiments, the •OH radical and the h+ were the main oxidizing agents for the BAM. Overall, the biodegradable photocatalytic composites are a reliable and a low-cost alternative to eliminate pesticides from the drinking water and can find application in water purification processes.

Control of the asymmetric growth of nanowire arrays with gradient profiles.

A novel electrochemical methodology for the growth of arrays of Ni and Co nanowires (NWs) with linear and non-linear varying micro-height gradient profiles (µHGPs), has been developed. The growth mechanism of these microstructures consists of a three-dimensional growth originating from the allowed electrical contact between the electrolyte and the edges of the cathode at the bottom side of porous alumina membranes. It has been shown that the morphology of these microstructures strongly depends on electrodeposition parameters like the cation material and concentration and the reduction potential. At constant reduction potentials, linear Ni µHGPs with trapezoid-like geometry are obtained, whereas deviations from this simple morphology are observed for Co µHGPs. In this regime, the µHGPs average inclination angle decreases for more negative reduction potential values, leading as a result to more laterally extended microstructures. Besides, more complex morphologies have been obtained by varying the reduction potential using a simple power function of time. Using this strategy allows us to accelerate or decelerate the reduction potential in order to change the µHGPs morphology, so to obtain convex- or concave-like profiles. This methodology is a novel and reliable strategy to synthesize µHGPs into porous alumina membranes with controlled and well-defined morphologies. Furthermore, the synthesized low dimensional asymmetrically loaded nanowired substrates with µHGPs are interesting for their application in micro-antennas for localized electromagnetic radiation, magnetic stray field gradients in microfluidic systems, non-reciprocal microwave absorption, and super-capacitive devices for which a very large surface area and controlled morphology are key requirements.

Analytical magnetostatic model for 2D arrays of interacting magnetic nanowires and nanotubes.

A fully analytical model to describe the magnetostatic properties of these 2D nanocylinder arrays (tubes and wires) is presented. The model allows calculating the components of the effective demagnetizing field as a function of the cylinder height, inner and outer diameters, and the center-to-center distance. From these components, it is possible to calculate the shape anisotropy of the cylinder, the dipolar interaction between them, and the total magnetostatic energy. The model allows performing calculations very simply, using a simple spreadsheet or open-access software such as Geogebra. This allows analyzing the effect of each geometrical parameter in the different contributions to the magnetostatic energy. Amongst the most interesting findings is that the model describes naturally the magnetization easy-axis reorientation transition induced by the dipolar interaction, for which a general phase diagram has been calculated for both tubes and wires. For the case of nanowires, our results show a very good agreement with previously published results. While for nanotubes, the model predicts that the magnetization easy-axis reorientation transition is frustrated as the tube wall thickness decreases and reaches a critical value even when the distance between tubes is reduced to its lowest possible value.

Artificially modified magnetic anisotropy in interconnected nanowire networks.

Interconnected or crossed magnetic nanowire networks have been fabricated by electrodeposition into a polycarbonate template with crossed cylindrical nanopores oriented ±30° with respect to the surface normal. Tailor-made nanoporous polymer membranes have been designed by performing a double energetic heavy ion irradiation with fixed incidence angles. The Ni and Ni/NiFe nanowire networks have been characterized by magnetometry as well as ferromagnetic resonance and compared with parallel nanowire arrays of the same diameter and density. The most interesting feature of these nanostructured materials is a significant reduction of the magnetic anisotropy when the external field is applied perpendicular and parallel to the plane of the sample. This effect is attributed to the relative orientation of the nanowire axes with the applied field. Moreover, the microwave transmission spectra of these nanowire networks display an asymmetric linewidth broadening, which may be interesting for the development of low-pass filters. Nanoporous templates made of well-defined nanochannel network constitute an interesting approach to fabricate materials with controlled anisotropy and microwave absorption properties that can be easily modified by adjusting the relative orientation of the nanochannels, pore sizes and material composition along the length of the nanowire.

Supramolecular assemblies of nucleoside functionalized carbon nanotubes: synthesis, film preparation, and properties.

Nucleoside-functionalized multi-walled carbon nanotubes (N-MWCNTs) were synthesized and characterized. A self-organization process using hydrogen bonding interactions was then used for the fabrication of self-assembled N-MWCNTs films free of stabilizing agents, polymers, or surfactants. Membranes were produced by using a simple water-dispersion-based vacuum-filtration method. Hydrogen-bond recognition was confirmed by analysis with IR spectroscopy and TEM images. Restoration of the electronic conduction properties in the N-MWCNTs membranes was performed by removing the organic portion by thermal treatment under an argon atmosphere to give d-N-MWCNTs. Electrical conductivity and thermal gravimetric analysis (TGA) measurements confirmed the efficiency of the annealing process. Finally, oxidative biodegradation of the films N-MWCNTs and d-N-MWCNTs was performed by using horseradish peroxidase (HRP) and low concentrations of H2 O2 . Our results confirm that functional groups play an important role in the biodegradation of CNT by HRP: N-MWCNTs films were completely biodegraded, whereas for d-N-MWCNTs films no degradation was observed, showing that the pristine CNT undergoes minimal enzyme-catalyzed oxidation This novel methodology offers a straightforward supramolecular strategy for the construction of conductive and biodegradable carbon nanotube films.

Photoluminescence shift in frustules of two pennate diatoms and nanostructural changes to their pores.

The diatom silicified cell wall (frustule) contains pore arrays at the micro- to nanometer scale that display efficient luminescence within the visible spectrum. Morphometric analysis of the size and arrangement of pores was conducted to observe whether any correlation exists with the photoluminescence (PL) of two diatom species of different ages. UV-excited PL displays four clearly defined peaks within the blue-region spectrum, on top of the broad PL characteristic of synthetic porous silicon dioxide, recorded for reference and where discrete lines are absent. A set of shifted emission lines was observed when diatom cultures reached adulthood. These discrete line shifts correlate with structural changes observed in adult frustules: reduction in pore diameter; appearance of pores within pores, 10 nm in size; an increase in the gap distance between stria; and the deposition of several girdle bands with a concomitant increase in the diatom waist length, as well as the appearance of pores on such bands. Destruction of the pores results in the disappearance of all discrete emission lines. The PL shifts are correlated with a substantial increment of Si-OH groups adsorbed on the frustule surface, as revealed by Fourier transform infrared spectroscopy.

Effectiveness of bonding resin-based composite to healthy and fluorotic enamel using total-etch and two self-etch adhesive systems.

The aim of this study was to evaluate the bond strength of three adhesive systems: Excite™, Adper Prompt L-Pop™ and AdheSE One™ to varying degrees of fluorotic enamel using micro-tensile bond strength (µTBS) tests. Human enamel was classified according to the Thylstrup and Fejerskov Index. The interface resin-enamel was observed using stereoscopic and electron microscopy. The Excite™, achieved the highest µTBS when bonded to healthy enamel and decreased as the degree of fluorosis increased (p<0.05). The Prompt L-Pop™ improved the bonding on moderate and severe fluorosis. The µTBS of the AdheSE One™, was significantly lower in all degrees of fluorotic enamel (p<0.05) indicating a very poor bonding ability to enamel. These results will provide clinicians with preliminary data to assist them in the selection of the most effective adhesive systems for treatment of fluorosis enamel, resulting in more successful restorative care.

Electrodeposition growth of nanowire arrays with height gradient profiles for microwave device applications.

A simple and nonexpensive adapted dip-coating technique is presented and used to fabricate arrays of magnetic nanowires with a linear varying height profile. This approach allows controlling the wire height from tenths of nanometers up to several micrometers. Furthermore, the main parameters of this height gradient can be controlled, such as the maximum wire height and the lateral span of the wire array, which can be predicted with excellent accuracy using a proposed analytical model. Moreover, we show that by sequential electrodeposition with dip-coating, arrays of these height varying wires can be grown. This technique represents a novel method to fill porous templates with controlled spatial growth, leading to the fabrication of novel structures and providing control over structural features on the nanoscale level. In particular, the use of these asymmetrically loaded magnetic nanowired substrates to obtain improved microwave nonreciprocal behavior is shown for a microwave phase shifter.

Coupling of demixing and magnetic ordering phase transitions probed by turbidimetric measurements in a binary mixture doped with magnetic nanoparticles.

We present a novel study on the effect of a magnetic field applied on a binary mixture doped with magnetic nanoparticles close to its demixing transition. Turbidity measurements in the Faraday configuration show that the effect of applying an external field produces changes in the critical opalescence of the mixture that allow us to track an aggregation produced by critical Casimir forces and a reversible aggregation due to the formation of chain-like flocks in response to the external magnetic field. The observation of a crossover of the aggregation curves through optical signals is interpreted as the evolution from low to high power dispersion nuclei due to an increase in the radius of the condensation seed brought about by Casimir or magnetic interactions. Finally, evidence of an enhanced magnetocaloric effect due to the coupling between mixing and ordering phase transitions is presented which opens up a nonsolid state approach of designing refrigerating cycles and devices.