Redox-switchable chromophores based on metal (Ni, Pd, Pt) mixed-ligand dithiolene complexes showing molecular second-order nonlinear-optical activity

The synthesis and full characterization of the redox-active nickel triad mixed-ligand dithiolene complexes based on Bz(2)pipdt = 1,4-dibenzylpiperazine-3,2-dithione and dmit = 2-thioxo-1,3-dithiole-4,5-dithiolate ligands are reported. These complexes show a reversibly bleacheable solvatochromic peak and a remarkably high negative molecular first hyperpolarizability, whose values depend on the metal being highest for the platinum(II) compound.     

Development of catalytically active silver colloid nanoparticles stabilized by dextran

Colloidal silver nanoparticles (Ag-NPs) with a mean diameter of 6.1 nm and a narrow size distribution were prepared by reduction of the correspondent metal salt with injection of NaBH(4), in the presence of dextran, and characterized by UV-vis, TEM, and DLS. The concentration of all reactants involved in the formation of the nanoparticles was optimized with the use of a new multivariate method, which revealed a significant reduction in the number of experiments when compared with the vast majority of univariate methods described in the literature. The Ag-NPs-dextran composite was able to efficiently catalyze the p-nitrophenol reduction in water by NaBH(4) with a rate constant normalized to the surface area of the nanoparticles per unit volume (k(1)) of 1.41 s(-1) m(-2) L, which is higher than values ever reported for Ag-NPs catalytic systems.     

Nano-organization of amylose-b-polystyrene block copolymer films doped with bipyridine

This paper discusses the self-assembly of rod-coil amylose-b-polystyrene (Mal-b-PS) block copolymer thick and thin films. The nano-organization falls in an interdomain spacing d of about 10 nm, much smaller than flexible-flexible petrol block copolymer systems. Additionally, hydrogen-bonding interactions between carbohydrate rods (amylose) and 4',4-bipyridine (bipy) molecules induces phase transitions. Indeed, adding bipy in maltooctadecaose-block-polystyrene (Mal18-b-PS) copolymers results, at room temperature, in the formation of a lamellar phase having Mal18 bipy-rich nanodomains instead of hexagonal close-packed (HCP) of cylinders made of Mal18, whereas a coexistence of Mal7bipy-rich cylindrical and spherical nanodomains are formed from maltoheptaose-b-polystyrene (Mal7-b-PS) copolymers instead of a poorly organized array of Mal7-based cylinders. On heating, the Mal7bipy-b-PS system shows more rich phase behavior as compared to the Mal7-b-PS one due to weakening of hydrogen bonding with temperature. Such a system is of great interest in developing active layers in light-emitting diodes (LEDs) or in photovoltaic cells to realize devices with an optimal structure, that is, having large interface area and domain size with similar exciton diffusion length (10 nm).     

Laser-induced fluorescence and FT-Raman spectroscopy for characterizing patinas on stone substrates

This article reports on a compositional investigation of stone patinas: thin colored layers applied for protective and/or aesthetic purposes on architectural or sculptural substrates of cultural heritage. The analysis and classification of patinas provide important information of historic and artistic interest, as their composition reflects local practices, the availabilities of different materials, and the development of technological knowledge during specific historical periods. Model patinas fabricated according to traditional procedures and applied onto limestone, and a historic patina sample from the main façade of the San Blas Monastery in Lerma (a village in the province of Burgos, Spain), were analyzed by laser-induced fluorescence and Fourier transform Raman spectroscopy. The results obtained demonstrate the ability of these two analytical techniques to identify the key components of each formulation and those of the reaction products which result from the chemical and mineralogical transformations that occur during aging, as well as to provide information that can aid the classification of different types of patinas.

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Figure Cross section of model patina (left) and FT-Raman spectrum of historic patina from the façade of San Blas Monastery, Lerma, Burgos, Spain (right).

     

Enhanced shape-selective recognition of anion guests through complexation-induced organization of porphyrin hosts

We present a fortuitous discovery of enhanced shape-selective recognition of anion guests that stems from a complexation-induced conformational change in porphyrin hosts upon anion binding. Porphyrin hosts reported here exist in a conformation that is not favorable to guest binding. Anions that bind strongly are those that can induce a conformational change in the host to allow guest binding. Furthermore, guests that mimic the shape of the newly formed pocket bind the strongest.     

Airborne nanoparticle exposures associated with the manual handling of nanoalumina and nanosilver in fume hoods

Manual handling of nanoparticles is a fundamental task of most nanomaterial research; such handling may expose workers to ultrafine or nanoparticles. Recent studies confirm that exposures to ultrafine or nanoparticles produce adverse inflammatory responses in rodent lungs and such particles may translocate to other areas of the body, including the brain. An important method for protecting workers handling nanoparticles from exposure to airborne nanoparticles is the laboratory fume hood. Such hoods rely on the proper face velocity for optimum performance. In addition, several other hood design and operating factors can affect worker exposure. Handling experiments were performed to measure airborne particle concentration while handling nanoparticles in three fume hoods located in different buildings under a range of operating conditions. Nanoalumina and nanosilver were selected to perform handling experiments in the fume hoods. Air samples were also collected on polycarbonate membrane filters and particles were characterized by scanning electron microscopy. Handling tasks included transferring particles from beaker to beaker by spatula and by pouring. Measurement locations were the room background, the researcher’s breathing zone and upstream and downstream from the handling location. Variable factors studied included hood design, transfer method, face velocity/sash location and material types. Airborne particle concentrations measured at breathing zone locations were analyzed to characterize exposure level. Statistics were used to test the correlation between data. The test results found that the handling of dry powders consisting of nano-sized particles inside laboratory fume hoods can result in a significant release of airborne nanoparticles from the fume hood into the laboratory environment and the researcher’s breathing zone. Many variables were found to affect the extent of particle release including hood design, hood operation (sash height, face velocity), work practices, type and quantity of the material being handled, room conditions, and the adequacy of the room exhaust.

On evolutionary spatial heterogeneous games

How cooperation between self-interested individuals evolve is a crucial problem, both in biology and in social sciences, that is far from being well understood. Evolutionary game theory is a useful approach to this issue. The simplest model to take into account the spatial dimension in evolutionary games is in terms of cellular automata with just a one-parameter payoff matrix. Here, the effects of spatial heterogeneities of the environment and/or asymmetries in the interactions among the individuals are analysed through different extensions of this model. Instead of using the same universal payoff matrix, bimatrix games in which each cell at site (i, j) has its own different ‘temptation to defect’ parameter T(i,j) are considered. First, the case in which these individual payoffs are constant in time is studied. Second, an evolving evolutionary spatial game such that T=T(i,j;t), i.e. besides depending on the position evolves (by natural selection), is used to explore the combination of spatial heterogeneity and natural selection of payoff matrices.     

Investigation of laser ablation on hybrid sol–gel material applied to kinoform etching

Ultraviolet laser machining of a hybrid organic/inorganic material prepared via a sol–gel process has been studied for the fabrication of kinoforms or surface relief diffractive optical elements. The hybrid mixes silicon and titanium oxides and an organic network in order to improve the mechanical properties. Different material compositions have been investigated. Laser ablation of the hybrid material is observed at low laser fluence (measured threshold fluence of 125 mJ/cm² at 248 nm/6 ns) and shows that the process is well adapted to micro-patterning by laser machining means. The best observed depth resolution is 60± 20 nm and appears to be limited by the ablation setup. Finally, the fabrication of an effective diffractive optical element and its operation at 1.06 μm are described. PACS  81.20.Fw; 79.20.Ds; 42.79.-e     

Oxidative decarboxylation of arylacetic acids by means of tetrabutylammonium periodate

Tetrabutylammonium periodate (TBAPI) in refluxing dioxane is able to convert arylacetic acids into the corresponding nor-aldehydes in good yields.