Theoretical investigation of Cu5/silicates deposited on rutile TiO2 as a photocatalyst.

Titanium dioxide (TiO2) is an exceptional compound with unique optical properties, which have been intensively used for applications in photocatalysis. Recent studies show that Cu5 atomic quantum clusters (AQCs) could facilitate visible light absorption and enhance the photocatalytic properties of rutile TiO2 by creating mid-gap states. In this work, to move the theory of these catalysts closer to the experiment, we investigate the electronic structures of Cu5 adsorbed on a perfect and reduced rutile TiO2 surface in the absence and presence of silicate SiO32- ions, which are introduced for the purification of Cu5 AQCs. Encouragingly, our DFT simulations predict that the presence of SiO32- does not reduce the gap states of the Cu5@TiO2 composite and could even enhance them by shifting more states into the band gap. Our results also demonstrate that the polarons created by oxygen vacancies (Ov) and Cu5 coexist within the band gap of TiO2. Indeed an Ov behaves like a negative gate on the electronic states located on the AQCs, thereby shifting states out of the valence band into the band gap, which could lead to enhanced photocatalytic performance.

Stability and Reversible Oxidation of Sub-Nanometric Cu5 Metal Clusters: Integrated Experimental Study and Theoretical Modeling.

Sub-nanometer metal clusters have special physical and chemical properties, significantly different from those of nanoparticles. However, there is a major concern about their thermal stability and susceptibility to oxidation. In situ X-ray Absorption spectroscopy and Near Ambient Pressure X-ray Photoelectron spectroscopy results reveal that supported Cu5 clusters are resistant to irreversible oxidation at least up to 773 K, even in the presence of 0.15 mbar of oxygen. These experimental findings can be formally described by a theoretical model which combines dispersion-corrected DFT and first principles thermochemistry revealing that most of the adsorbed O2 molecules are transformed into superoxo and peroxo species by an interplay of collective charge transfer within the network of Cu atoms and large amplitude "breathing" motions. A chemical phase diagram for Cu oxidation states of the Cu5 -oxygen system is presented, clearly different from the already known bulk and nano-structured chemistry of Cu.

Synthesis of photocatalytic cysteine-capped Cu≈10 clusters using Cu5 clusters as catalysts.

We report an easily scalable synthesis method for the preparation of cysteine-capped Cu≈10 clusters through the reduction of Cu(II) ions with NaBH4, using Cu5 clusters as catalysts. The presence of such catalytic clusters allows controlling the formation of the larger Cu≈10 clusters and prevents the production of copper oxides or Cu(I)-cysteine complexes, which are formed when Cu5 is absent or at lower concentrations, respectively. These results indicate that small catalytic clusters could be involved, as precursor species before the reduction step, in the different methods developed for the synthesis of clusters. The visible light-absorbing Cu≈10 clusters, obtained by the cluster-catalysed method, display high photocatalytic activities for the decomposition of methyl orange with visible light.

Gold nanorod synthesis catalysed by Au clusters.

Gold nanorods have been successfully synthesized by the seed mediated method using Au clusters. This synthesis does not require silver ions to obtain large amounts of Au nanorods and has good control over their aspect ratio. Au clusters are produced with the same recipe as for Au seeds, but using shorter reaction times. This very simple scheme confirms the important catalytic influence of clusters in the anisotropic growth control.

Biodistribution of polyacrylic acid-coated iron oxide nanoparticles is associated with proinflammatory activation and liver toxicity.

Iron oxide nanoparticles (IONs) have physical and chemical properties that render them useful for several new biomedical applications. Still, so far, in vivo safety studies of IONs with coatings of biomedical interest are still scarce. The aim of this study, therefore, was to clarify the acute biological effects of polyacrylic acid (PAA)-coated IONs, by determining their biodistribution and their potential proinflammatory and toxic effects in CD-1 mice. The biodistribution of PAA-coated IONs in several organs (liver, spleen, kidneys, brain, heart, testes and lungs), the plasma cytokines, chemokine and aminotransferases levels, white blood cell count, oxidative stress parameters, adenosine triphosphate and histologic features of liver, spleen and kidneys were evaluated 24 h after a single acute (8, 20 or 50 mg kg(-1) ) intravenous administration of PAA-coated IONs in magnetite form. The obtained results showed that these IONs accumulate mainly in the liver and spleen and, to a lesser extent, in the lungs. Although our data showed that PAA-coated IONs do not cause severe organ damage, an inflammatory process was triggered in vivo, as evidenced by as evidenced by increased neutrophils and large lymphocytes in the differential blood count. Moreover, an accumulation of iron in macrophages of the liver and spleen was observed and hepatic lipid peroxidation was elicited, showing that the IONs are able to induce oxidative stress. The effects of these nanoparticles need to be further investigated regarding the mechanisms involved and the long-term consequences of intravenous administration of PAA-coated IONs. Copyright © 2016 John Wiley & Sons, Ltd.

Controlling Bimetallic Nanostructures by the Microemulsion Method with Subnanometer Resolution Using a Prediction Model.

We present a theoretical model to predict the atomic structure of Au/Pt nanoparticles synthesized in microemulsions. Excellent concordance with the experimental results shows that the structure of the nanoparticles can be controlled at subnanometer resolution simply by changing the reactant concentration. The results of this study not only offer a better understanding of the complex mechanisms governing reactions in microemulsions, but open up a simple new way to synthesize bimetallic nanoparticles with ad hoc controlled nanostructures.

Polyacrylic acid-coated and non-coated iron oxide nanoparticles induce cytokine activation in human blood cells through TAK1, p38 MAPK and JNK pro-inflammatory pathways.

Iron oxide nanoparticles (ION) can have a wide scope of applications in biomedicine, namely in magnetic resonance imaging, tissue repair, drug delivery, hyperthermia, transfection, tissue soldering, and as antimicrobial agents. The safety of these nanoparticles, however, is not completely established, namely concerning their effect on immune system and inflammatory pathways. The aim of this study was to evaluate the in vitro effect of polyacrylic acid (PAA)-coated ION and non-coated ION on the production of six cytokines [interleukin 1 beta (IL-1ß), tumor necrosis factor alpha (TNF-α), interleukin 6 (IL-6), interleukin 8 (IL-8), interferon gamma (IFN-γ) and interleukin 10 (IL-10)] by human peripheral blood cells, and to determine the inflammatory pathways involved in this production. The obtained results showed that PAA-coated and non-coated ION were able to induce all the tested cytokines and that activation of transforming growth factor beta (TGF-ß)-activated kinase (TAK1), p38 mitogen-activated protein kinases (p38 MAPK) and c-Jun N-terminal kinases (JNK) were involved in this effect.

Ag2 and Ag3 clusters: synthesis, characterization, and interaction with DNA.

Subnanometric samples, containing exclusively Ag2 and Ag3 clusters, were synthesized for the first time by kinetic control using an electrochemical technique without the use of surfactants or capping agents. By combination of thermodynamic and kinetic measurements and theoretical calculations, we show herein that Ag3 clusters interact with DNA through intercalation, inducing significant structural distortion to the DNA. The lifetime of Ag3 clusters in the intercalated position is two to three orders of magnitude longer than for classical organic intercalators, such as ethidium bromide or proflavine.

Structure-directing and high-efficiency photocatalytic hydrogen production by Ag clusters.

H2 production by water splitting is hindered mainly by the lack of low-cost and efficient photocatalysts. Here we show that sub-nanometric silver clusters can catalyze the anisotropic growth of gold nanostructures by preferential adsorption at certain crystal planes of Au seeds, with the result that the final nanostructure can be tuned via the cluster/seed ratio. Such semiconducting Ag clusters are extremely stable and retain their electronic structure even after adsorption at the tips of Au nanorods, enabling various photocatalytic experiments, such as oxygen evolution from basic solutions. In the absence of electron scavengers, UV irradiation generates photoelectrons, which are stored within the nanorods, increasing their Au Fermi level up to the redox pinning limit at 0 V (RHE), where hydrogen evolution occurs with an estimated high efficiency of 10%. This illustrates the considerable potential of very small zerovalent, nonmetallic clusters as novel atomic-level photocatalysts.

Green emitter copper clusters as highly efficient and reusable visible degradation photocatalysts.

Green emitter copper clusters (CuCLs) with a size of ≈1.5 nm can be used as very efficient and recyclable photocatalysts for the degradation of methylene blue, both in solution and supported onto glass surface showing a photocatalytic efficiency larger than that found with common semiconductors. These results open a new important potential way to overcome major difficulties found in the photocatalysis field with the common semiconductors.

Thermal annealing as an easy tool for the controlled arrangement of gold nanoparticles in block-copolymer thin films.

Thermal annealing was used for the bottom-up fabrication of morphologically controlled gold-block-copolymer (Au-BC) nanocomposites. Three different blends formed by polystyrene (PS) homopolymer and PS-coated gold nanoparticles (PSSH@Au) were used as modifiers of asymmetric polystyrene-b-polymethylmethacrylate (PS-b-PMMA): PS26/PS26SH@Au, PS75/PS75SH@Au and PS167/PS167SH@Au (where the subscripts refer to the number of styrene monomeric units).The results indicated that all three blends used as modifiers (PSn/PSnSH@Au) were successfully located in the PS phase during thermally induced BC self-assembly for a composition range from 5 to 43 wt% without macro-phase separation. The PSnSH@Au moiety experienced molecular desorption, nanocrystal core coalescence and partial molecular re-encapsulation processes during thermal annealing, leading to sphere-like gold NPs with a larger average size (without exceeding an interdomain distance). Ligand chain length regulated the degree of coalescence and re-encapsulation, defining ultimate core size. Furthermore, proper combination of chain length and composition enabled tuning of NP partitioning and arrangement on different length scales through thermally activated cooperative assembly processes. These results have not only significant impact for establishing thermal processing as a useful tool for the precise control of NP size and distribution, but also much broader implications for many nanoparticle-based technologies.

Plastic matters: an analytical procedure to evaluate the degradability of contemporary works of art.

The most significant results concerning a chemical study to evaluate the degradability of polymeric components in four contemporary works of art, partially or completely realized in plastics, are presented and discussed in this paper. The procedure applied is mainly based on the use of Fourier transform IR and UV-vis spectroscopies and pyrolysis-gas chromatography/mass spectrometry, and consists of the following steps: (1) compositional analysis of the artworks, with particular attention to components which may have a negative effect on the overall ageing; (2) evaluation of the actual state of conservation; (3) investigation of the accelerated ageing of reference polymer samples; and (4) monitoring of the natural ageing of the artworks. On such a basis, the following could be concluded. Stage Evidence by Loris Cecchini is made of poly(ether urethane) elastomer which contains a high amount of phthalates. Their exudation gives a sticky appearance to the artwork and their removal during ageing is the main cause of the loss of flexibility. The latex used by Andrés Pinal for tailoring Traxe de Home is a natural polyisoprene, whose oxidative degradation accounts for the extensive deterioration and yellowing of the artwork. The plaster sculptures of 3D Bodyscans 1:9 by Karin Sander are coated with an aliphatic epoxy resin. Its oxidation with formation of amides is the cause of the surface yellowing. The adhesive used by Dario Villalba for Tierra, Ladrillo y Agua is a commercial poly(vinyl acetate). Simulated photoageing suggests a fast deterioration due to deacetylation and cross-linking, which possibly is the main reason for the actual detachment of debris from the support.

One step synthesis of the smallest photoluminescent and paramagnetic PVP-protected gold atomic clusters.

Gold atomic clusters of only two and three atoms were prepared by a simple electrochemical technique based on the anodic dissolution of a gold electrode in the presence of PVP, and subsequent electroreduction of the Au-PVP complexes. These clusters show stable photoluminescent and magnetic properties, which make them the smallest and most elemental gold (0) building blocks in nature (after atoms) bringing new possibilities to construct novel nano/microstructures with large potential interest in biomedicine, catalysis, and so forth.

A Simple Entropic-Driving Separation Procedure of Low-Size Silver Clusters, Through Interaction with DNA.

Synthesis and purification of metal clusters without strong binding agents by wet chemical methods are very attractive for their potential applications in many research areas. However, especially challenging is the separation of uncharged clusters with only a few number of atoms, which renders the usual techniques very difficult to apply. Herein, we report the first efficient separation of Ag2 and Ag3 clusters using the different entropic driving forces when such clusters interact with DNA, into which Ag3 selectively intercalates. After sequential dialysis of the samples and denaturalizing the DNA-Ag3 complex, pure Ag2 can be found in the dialysate after extensive dialysis. Free Ag3 is recovered after DNA denaturation.

Silver sub-nanoclusters electrocatalyze ethanol oxidation and provide protection against ethanol toxicity in cultured mammalian cells.

Silver atomic quantum clusters (AgAQCs), with two or three silver atoms, show electrocatalytic activities that are not found in nanoparticles or in bulk silver. AgAQCs supported on glassy carbon electrodes oxidize ethanol and other alcohols in macroscopic electrochemical cells in acidic and basic media. This electrocatalysis occurs at very low potentials (from approximately +200 mV vs RHE), at physiological pH, and at ethanol concentrations that are found in alcoholic patients. When mammalian cells are co-exposed to ethanol and AgAQCs, alcohol-induced alterations such as rounded cell morphology, disorganization of the actin cytoskeleton, and activation of caspase-3 are all prevented. This cytoprotective effect of AgAQCs is also observed in primary cultures of newborn rat astrocytes exposed to ethanol, which is a cellular model of fetal alcohol syndrome. AgAQCs oxidize ethanol from the culture medium only when ethanol and AgAQCs are added to cells simultaneously, which suggests that cytoprotection by AgAQCs is provided by the ethanol electro-oxidation mediated by the combined action of AgAQCs and cells. Overall, these findings not only show that AgAQCs are efficient electrocatalysts at physiological pH and prevent ethanol toxicity in cultured mammalian cells, but also suggest that AgAQCs could be used to modify redox reactions and in this way promote or inhibit biological reactions.

Tailored surface composition of Au/Pt nanocatalysts synthesized in microemulsions: a simulation study.

Au/Pt nanoparticles show an optimized catalytic activity when compared with Pt nanoparticles because Pt activity is improved by the presence of Au on the surface. It was checked whether a controllable surface composition can be achieved by the simple strategy of varying the Au : Pt ratio. We present an in-depth kinetic simulation study on the influence of Au : Pt ratio on the formation of Au/Pt nanoparticles synthesized in microemulsions. This study is able to explain the resulting nanoarrangement as a function of kinetic parameters such as Au : Pt ratio and intermicellar exchange rate. The role of the micelles as a dosing pump of the Au precursor explains that a higher Au amount results in a Au reduction which takes place over a longer period of time. It implies that Au is deposited until longer stages of the synthesis, so Au is present at the nanoparticle surface. Micelles as reaction media produce a minor impact on Pt due to its slower reduction. These different kinetic behaviours of Au and Pt give rise to a surface composition which can be tailored by tuning the Au : Pt ratio. Numerical results on surface composition successfully reproduce experimental data and further support the outcomes of the degree of atomic mixing under different Au : Pt ratios.

Competing magnetism and superconductivity in Na(x)CoO2 at half doping.

We report the effect of topotactic replacement of Na(+) by H(3)O(+) in Na(0.5)CoO(2). Hydronium ions keep the Co oxidation state constant, increasing the interlayer distance. The result is a progressive destruction of the spin density wave characteristic of half-doped Na(x)CoO(2) and ultimately the induction of superconductivity. This implies that superconductivity occurs closer to Co(3+)/Co(4+) approximately = 1 than previously thought and that its development competes with the development of the magnetic phase.