Extrinsic Point Defects in TiO2-Acetylacetone Charge-Transfer Complex and Their Effects on Optical and Photochemical Properties.

TiO2-based visible-light-sensitive nanomaterials are widely studied for photocatalytic applications under UV-Vis radiation. Among the mechanisms of visible-light sensitization, extrinsic oxygen vacancies have been introduced into TiO2 and charge-transfer complexes (CTCs) have been formed between chelating ligands, such as acetylacetone, and nanocrystalline TiO2 (TiO2-ACAC). However, the influence of extrinsic oxygen vacancies on the photocatalytic performance of TiO2-based CTCs is unknown. In this work, surface/bulk extrinsic oxygen vacancies were introduced into TiO2-ACAC through calcination at 270 °C under static air, argon, and hydrogen atmospheres. TiO2-ACAC CTCs were characterized by X-ray powder diffraction, thermogravimetric analysis, diffuse-reflectance spectroscopy, photoluminescence, electron paramagnetic resonance (EPR), and X-ray photoelectron spectroscopy techniques. The correlation between EPR-spin trapping and tetracycline (TC) photodegradation, using scavengers, highlighted the key role of the superoxide radical in TC degradation by TiO2-ACAC CTCs under low-power visible-light radiation. The increased extrinsic oxygen vacancies concentration was not beneficial for the photocatalytic performance of TiO2 CTCs, since bulk extrinsic oxygen vacancies additionally act as recombination centers. In fact, the TiO2-ACAC CTC with the lowest extrinsic oxygen vacancies concentration exhibited the highest photocatalytic performance for TC degradation due to an adequate distribution of extrinsic bulk oxygen vacancies, which led to the trapped electrons undergoing repeated hopping, reducing the recombination rates and improving the efficiency in superoxide radicals production. Our findings indicated that TiO2-ACAC CTCs are able to degrade pollutants via interactions with electronic holes and principally superoxide radicals and also, provided fundamental information about the influence of surface/bulk extrinsic oxygen vacancies on the photocatalytic performance, lattice parameters, and optical and photochemical properties of TiO2-based CTCs.

Silver-modified nitrogen-doped graphene quantum dots as a sensor for formaldehyde in milk using headspace micro-extraction on a single-drop of aqueous nanoparticles dispersion.

BACKGROUND: Fraudulent practices used to distort the quality of milk and derivatives include the addition of formaldehyde. RESULTS: A formaldehyde sensor was developed based on the luminescence of newly proposed N-doped graphene quantum dots modified with silver (N-GQDs-Ag) that were prepared using a simple method. A microdroplet of the nanoparticle dispersion was used to collect formaldehyde vapor by headspace single-drop micro-extraction (HS-SDME). After, the microdroplet was diluted in water, the nanoparticle photoluminescence quenching, caused by the analyte, was measured. The strong luminescent quenching allowed a detection limit at 1.7 × 10-4% w/v. Response was selective towards formaldehyde. SIGNIFICANCE: The method was effective and a cost-effective method for screening analysis of milk samples with matrix interferences minimized due to the nature of nanoparticle (prepared using Tollen's reagent) and due to the probing at the headspace of the sample cell. Results were statistically similar to those obtained using liquid chromatography.

On the physicochemical origin of nanoscale friction: the polarizability and electronegativity relationship tailoring nanotribology.

Friction is a ubiquitous manifestation of nature, and when it is studied at the nanoscale, complex and interesting effects arise from fundamental physical and chemical surface properties. Surprisingly, and probably due to the complexity of nanofriction studies, this aspect has not been completely discussed in prior studies. To fully consider the physicochemical influence in nanoscale friction, amorphous carbon films with different amounts of hydrogen and fluorine were prepared, chemically characterized, and evaluated via lateral force microscopy. Hydrogen and fluorine were selected because although they exhibit different physicochemical properties, both contribute to frictional force reduction. Indeed, to explain the experimental behavior, it is necessary to propose a new damping constant unifying both polarizability (physical) and electronegativity (chemical) properties. The satisfactory agreement between theory and experiments may encourage and enhance deeper discussion and new experiments that take into account the chemical peculiarities of frictional behavior relating to nanoscale elastic regimes.

Stereometric analysis of Amazon rainforest Anacardium occidentale L. leaves.

MAIN CONCLUSION: AFM, profilometry and SEM measurements on both sides of the Anacardium occidentale L. leaf reveal that ultrastructure presented some singularities due to their different morphologies and roughness. The advanced stereometry and power spectrum density of both sides of the Anacardium occidentale L. leaf were carefully studied. We use three different microscopy techniques such as scanning electron microscopy, profilometry, and atomic force microscopy for a complete description of the leaf surface morphology. The morphology of the adaxial and abaxial sides revealed a surface composed of striated cuticles and stomata cells, respectively. The height parameters obtained by profilometry revealed that the abaxial side was rougher. However, both sides presented similar Gaussian height distribution and asymmetry. The advanced stereometric parameters obtained by the topographic maps of AFM revealed that the two sides have some singularities due to their different morphologies and roughness, but with similar microtextures. However, average PSD spectra showed that adaxial and abaxial sides are dominated by relatively low and high spatial frequencies, showing that the microtextures, unlike what was shown in stereometric parameters, are different. These results revealed that leaves surface morphology under different aspects and scales and the quantitative parameters confirmed the different spatial patterns displayed, which can be of great interest for the study of the biological behavior of plants from their leaves.

CVD graphene/Ge interface: morphological and electronic characterization of ripples.

Graphene grown directly on germanium is a possible route for the integration of graphene into nanoelectronic devices as well as it is of great interest for materials science. The morphology of the interface between graphene and germanium influences the electronic properties and has not already been completely elucidated at atomic scale. In this work, we investigated the morphology of the single-layer graphene grown on Ge substrates with different crystallographic orientations. We determined the presence of sinusoidal ripples with a single propagation direction, zig-zag, and could arise due to compressive biaxial strain at the interface generated as a result of the opposite polarity of the thermal expansion coefficient of graphene and germanium. Local density of states measurements on the ripples showed a linear dispersion relation with the Dirac point slightly shifted with respect to the Fermi energy indicating that these out-of-plane deformations were n-doped, while the graphene regions between the highs were undoped.

Ice as a Green-Structure-Directing Agent in the Synthesis of Macroporous MWCNTs and Chondroitin Sulphate Composites.

The incorporation of multi-walled carbon nanotubes (MWCNTs) into chondroitin sulphate-based scaffolds and the effect on the structural, mechanical, conductive, and thermal properties of the resulting scaffolds is investigated. Three-dimensional hierarchical materials are prepared upon the application of the ice segregation-induced self-assembly (ISISA) process. The use of ice as structure-directing agents avoids chemicals typically used for this purpose (e.g., surfactants, block copolymers, etc.), hence, emphasising the green features of this soft-templating approach. We determine the critical parameters that control the morphology of the scaffolds formed upon ice-templating (i.e., MWCNTs type, freezing conditions, polymer and MWCNT concentration). MWCNTs are surface functionalized by acidic treatment. MWCNT functionalization is characterized by Raman, Fourier transfer infrared (FTIR) and X-ray Photoelectron (XPS) spectroscopies. Scanning electron microscopy (SEM) analysis and porosity studies reveal that MWCNT content modifies the morphology of the macroporous structure, which decreases by increasing MWCNT concentration. Differences in scaffold morphology should be translated into their conductivity and mechanical properties. As a general trend, the Young's modulus and the electrical conductivity of the scaffolds increase with the MWCNT content. Preliminary biocompatibility tests with human osteoblast-like cells also reveal the capability of these structures to support cell growth.