Organic–inorganic bonding in chitosan–silica hybrid networks: Physical properties

Novel biomaterials are needed for bone tissue repair with improved mechanical performance compared to classical bioceramics. The objective of this work was to characterize a hybrid filler material, which is capable to coat as a thin film porous scaffolds improving their mechanical properties for bone tissue engineering. The hybrid filler material is a blend of chitosan and silica network formed through in situ sol–gel using tetraethylortosilicate and 3‐glycidoxypropyltrimethoxysilane (GPTMS) as silica precursors. The hypothesis was that the epoxy ring of GPTMS could react with the amino groups of chitosan in acidic media while it is also reacting the siloxane groups of hydrolyzed silica precursors. The formation of the hybrid organic–inorganic network was assessed by different physical techniques revealing changes in molecular mobility and hydrophilicity upon chemical reaction. Finally, the cytotoxicity of the samples was also evaluated by MTT assay. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1391–1400     

Asymmetric Synthesis of Fluorinated Isoindolinones through Palladium‐Catalyzed Carbonylative Amination of Enantioenriched Benzylic Carbamates

The asymmetric synthesis of fluorinated isoindolinones has been achieved by a palladium‐catalyzed aminocarbonylation reaction of the corresponding α‐fluoroalkyl o‐iodobenzylamines. A base‐mediated anti β‐hydride elimination process was suggested to explain the partial erosion of the optical purity observed in some cases. This mechanistic rationale enabled the minimization of this partial racemization by fine‐tuning the pK_a of the base.     

Application of Atmospheric Solids Analysis Probe Mass Spectrometry (ASAP-MS) in Petroleomics: Analysis of Condensed Aromatics Standards,Crude Oil,and Paraffinic Fraction

Atmospheric solids analysis probe mass spectrometry (ASAP-MS) is a powerful tool for analysis of solid and liquid samples. It is an excellent alternative for crude oil analysis without any sample preparation step. Here, ASAP-MS in positive ion mode, ASAP(+)-MS, has been optimized for analysis of condensed aromatics (CA) standards, crude oil, and paraffinic fraction samples using a Synapt G2-S HDMS. Initially, two methodologies were used to access the chemical composition of samples: (1) using a temperature gradient varying from 150 to 600 °C at a heating rate of 150 °C min^–1, and (2) with constant temperature of 300 and 400 °C. ASAP(+)-MS ionized many compounds with a typical petroleum profile, showing a greater signals range of m/z 250–1300 and 200–1400 for crude oil and paraffin samples, respectively. Such performance, mainly related to the detection of high molecular weight compounds (>1000 Da), is superior to that of other traditional ionization sources, such as ESI, APCI, DART, and DESI. Additionally, the CA standards were identified in both forms: radicals, [M]^+?, and protonated cations, [M + H]⁺, with minimum fragmentation. Therefore, ASAP was more efficient in accessing the chemical composition of nonpolar and polar compounds. It is promising in its application with ultrahigh resolution MS instruments, such as FT-ICR MS and Orbitrap, since molecular formulas with greater resolution and mass accuracy (<1 ppm) would be assigned.

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Effect of Concentration on the Photophysics of Dyes in Light‐Scattering Materials.

Photoactive materials based on dye molecules incorporated into thin films or bulk solids are useful for applications as photosensitization, photocatalysis, solar cell sensitization and fluorescent labeling, among others. In most cases, high concentrations of dyes are desirable to maximize light absorption. Under these circumstances, the proximity of dye molecules leads to the formation of aggregates and statistical traps, which dissipate the excitation energy and lower the population of excited states. The search for enhancement of light collection, avoiding energy wasting requires accounting the photophysical parameters quantitatively, including the determination of quantum yields, complicated by the presence of light scattering when particulate materials are considered. In this work we summarize recent advances on the photophysics of dyes in light‐scattering materials, with particular focus on the effect of dye concentration. We show how experimental reflectance, fluorescence and laser‐induced optoacoustic spectroscopy data can be used together with theoretical models for the quantitative evaluation of inner filter effects, fluorescence and triplet formation quantum yields and energy transfer efficiencies.     

Numerical simulation of transpiration cooling through porous material

Transpiration cooling using ceramic matrix composite materials is an innovative concept for cooling rocket thrust chambers. The coolant (air) is driven through the porous material by a pressure difference between the coolant reservoir and the turbulent hot gas flow. The effectiveness of such cooling strategies relies on a proper choice of the involved process parameters such as injection pressure, blowing ratios, and material structure parameters, to name only a few. In view of the limited experimental access to the subtle processes occurring at the interface between hot gas flow and porous medium, reliable and accurate simulations become an increasingly important design tool. In order to facilitate such numerical simulations for a carbon/carbon material mounted in the side wall of a hot gas channel that are able to capture a spatially varying interplay between the hot gas flow and the coolant at the interface, we formulate a model for the porous medium flow of Darcy–Forchheimer type. A finite‐element solver for the corresponding porous medium flow is presented and coupled with a finite‐volume solver for the compressible Reynolds‐averaged Navier–Stokes equations. The two‐dimensional and three‐dimensional results at Mach number Ma = 0.5 and hot gas temperature T_HG=540 K for different blowing ratios are compared with experimental data. Copyright © 2014 John Wiley & Sons, Ltd.     

Spectrofluorimetric Determination Of Indium with 1,2,4-Trihydroxyanthraquinone

A new method for the spectrofluorimetric determination of indium by formation of a fluorescent 1:1 complex with 1,2,4-trihydroxyanthraquinone is proposed. The complex is formed in a mixed, 60:40 v/v acetone-water medium at pH 3.8 provided by an acetic acid-sodium acetate buffer. The calibration graph is linear between 10 and 600 ng/ml. The effect of potential interferents on the determination was assessed and the proposed method was applied to the determination of indium in synthetic samples.     

Compensation of second-order dispersion in femtosecond pulses after filamentation using volume holographic transmission gratings recorded in dichromated gelatin

We have designed and developed a pulse compressor with volume transmission holographic gratings to be implemented in post-compression experiments based on filamentation in gases. Pulse compression down to 13?fs has been demonstrated. The gratings have been recorded in commercial PFG-04 dichromated gelatin emulsions with a recording wavelength of 532?nm, attaining sufficient index modulation to achieve high efficiency when they are illuminated by an 800-nm laser.