Synthesis and hydrogen adsorption properties of a new iron based porous metal-organic framework

A new metal-organic framework [Fe₃O(OOC-C₆H₄-COO)₃(H₂O)₃]Cl·(H₂O)_x was synthesized with a specific surface area of 2823 m²/g and a lattice parameter of 88.61 Å. Isostructural with MIL-101, this compound exhibits similar hydrogen adsorption properties, with maximum adsorption capacity of 5.1wt.% H at 77 K. The adsorption enthalpy of hydrogen for MIL-101 and ITIM-1 (MIL-101Fe) at zero coverage was calculated for a wide temperature range of 77 K ÷ 324 K, considering corrections for the variation of hydrogen gas entropy with the temperature. The resulted adsorption enthalpy is 9.4 kJ/mol for MIL-101, in excellent agreement with the value reported in literature from microcalorimetric measurements, and a value of 10.4 kJ/mol at zero coverage was obtained for ITIM-1 (MIL-101Fe).     

Magnesia supported Au and Ag catalysts for the preparation of few-layer graphene–metal nanocomposites: relationship between catalyst structure and the properties of graphene composites

Magnesia supported Au, Ag, and Au–Ag nanostructured catalysts were prepared, characterized, and used to synthesize few-layer graphene–metal nanoparticle (Gr–MeNP) composites. The catalysts have a mezoporous structure and a mixture of MgO and MgO·H₂O as support. The gold nanoparticles (AuNPs) are uniformly dispersed on the surface of the Au/MgO catalysts, and have a uniform round shape with a medium size of ~8 nm. On the other hand, the silver nanoparticles (AgNPs) present on the Ag/MgO catalyst have an irregular shape, larger diameters, and less uniform dispersion. The Au–Ag/MgO catalyst contains large Au–Ag bimetallic particles of ~20–30 nm surrounded by small (5 nm) AuNPs. Following the RF-CCVD process and the dissolution of the magnesia support, relative large, few-layer, wrinkled graphene sheets decorated with metal nanoparticles (MeNPs) are observed. Graphene–gold (Gr–Au) and graphene–silver (Gr–Ag) composites had 4–7 graphitic layers with a relatively large area and similar crystallinity for samples prepared in similar experimental conditions. Graphene–gold–silver composites (Gr–Au–Ag) presented graphitic rectangles with round, bent edges, higher crystallinity, and a higher number of layers (8–14). The MeNPs are encased in the graphitic layers of all the different samples. Their size, shape, and distribution depend on the nature of the catalyst. The AuNPs were uniformly distributed, had a size of about 15 nm, and a round shape similar to those from Au/MgO catalyst. In Gr–Ag, the AgNPs have a round shape, very different from that of the Ag/MgO catalyst, large size distribution and are not uniformly distributed on the surface. Agglomerations of AgNPs together with large areas of pristine few-layer graphene were observed. In Gr–Au–Ag composites, almost exclusively large bimetallic particles of about 25–30 nm, situated at the edge of graphene rectangles have been found.     

Preconditioned Conjugate Gradient and Multigrid Methods for Numerical Solution of Multicomponent Mass Transfer Equations I. Diffusion-Reaction Equations

In a series of two papers, we analyze the numerical performances of the preconditioned conjugate gradient algorithms (BICGSTAB and GMRES) and multigrid method in solving two-dimensional multicomponent mass transfer equations. The present test problems are steady-state, linear and nonlinear diffusion-reaction equations. The nonlinear algorithm used in connection with the preconditioned conjugate gradient methods is the modified Picard iteration. Theoretical results about the preconditioning are presented. The multigrid algorithm used is the Full Approximation Storage algorithm. The finite difference method was used to discretize the mathematical model equations. The numerical results obtained show good numerical performances.     

Efficient photochromic transformation of a new fluorenyl diarylethene: one- and two-photon absorption spectroscopy

Efficient reversible phototransformation of a new diarylethene-fluorene derivative, 1,2-bis(5-(9,9-didecyl-7-nitro-9H-fluoren-2-yl)-2-methylthiophen-3-yl)cyclopent-1-ene (1), was demonstrated in organic media under low-intensity laser excitation. Linear photophysical characterization of 1 was performed at room temperature in solvents of different polarity and viscosity. Significantly, close to unity quantum yield for the cyclization reaction of 1 was shown in nonpolar solutions. The lifetimes of the excited states of the open (OF) and closed (CF) forms of 1 were measured by a femtosecond transient absorption technique, and corresponding values of ～0.7 and ～0.9 ps were shown in dichloromethane (DCM), respectively. Degenerate two-photon absorption (2PA) spectra of the OF and CF of 1 were obtained over a broad spectral range by the open aperture Z-scan method under 1 kHz femtosecond excitation. The values of 2PA cross sections of the OF in DCM (～50-70 GM) were found to increase up to 1 order of magnitude (～600 GM) after cyclization to the CF. The nature of cyclization and cylcoreversion processes were investigated by quantum chemistry with employment of DFT-based methods implemented in the Gaussian'09 program. The potential of 1 for application in optical data storage was shown using poly(methyl methacrylate)-doped films and two-photon fluorescence microscopy readout.     

Gold-silver alloy nanoshells: a new candidate for nanotherapeutics and diagnostics

We have developed novel gold-silver alloy nanoshells as magnetic resonance imaging (MRI) dual T₁ (positive) and T₂ (negative) contrast agents as an alternative to typical gadolinium (Gd)-based contrast agents. Specifically, we have doped iron oxide nanoparticles with Gd ions and sequestered the ions within the core by coating the nanoparticles with an alloy of gold and silver. Thus, these nanoparticles are very innovative and have the potential to overcome toxicities related to renal clearance of contrast agents such as nephrogenic systemic fibrosis. The morphology of the attained nanoparticles was characterized by XRD which demonstrated the successful incorporation of Gd(III) ions into the structure of the magnetite, with no major alterations of the spinel structure, as well as the growth of the gold-silver alloy shells. This was supported by TEM, ICP-AES, and SEM/EDS data. The nanoshells showed a saturation magnetization of 38 emu/g because of the presence of Gd ions within the crystalline structure with r₁ and r₂ values of 0.0119 and 0.9229 mL mg^-1 s^-1, respectively (Au:Ag alloy = 1:1). T₁- and T₂-weighted images of the nanoshells showed that these agents can both increase the surrounding water proton signals in the T₁-weighted image and reduce the signal in T₂-weighted images. The as-synthesized nanoparticles exhibited strong absorption in the range of 600-800 nm, their optical properties being strongly dependent upon the thickness of the gold-silver alloy shell. Thus, these nanoshells have the potential to be utilized for tumor cell ablation because of their absorption as well as an imaging agent.     

Rheological Aspects of Spanish Honeys

The purpose of this work was to investigate the rheological behavior of Spanish honeys under different conditions (at different temperatures and concentrations). All the samples were characterized to determine their physicochemical (moisture, ⁰Brix, pH, ash, conductivity, color, total acidity, diastase activity, 5-hydroxymethylfurfural content, sugar content) and thermal (glass transition temperature) profiles. The honeys samples (80.4–82 ⁰Brix) behaved as Newtonian fluid; as expected, their viscosity increased with the solid content and decreased with the temperature. Two experimental viscosity models (Arrhenius and Vogel–Taumman–Fulcher) were checked using the experimental data to correlate the influence of temperature on honey viscosity. A simplified model was proposed to describe the combined effect of the temperatures and concentrations (⁰Brix) on the viscosity of Spanish honeys. The dynamic viscosity and complex viscosity had the same magnitude at 40 °C, 45 °C, and 50 °C for of all the samples and the Cox Merz rule could be applied at these temperatures.     

Phase Transfer Catalysis in Phosphorus Chemistry

Phase-transfer catalysis (PTC) has been widely used for the synthesis of organic compounds for more than three decades. The scope and mechanistic features of PTC have been the aim of numerous studies. This review focuses on the application of phase transfer catalysis in synthesis of phosphorus compounds.     

Unsteady heat transfer from an elliptic cylinder

Numerical methods are used to investigate the transient heat transfer from an elliptic cylinder to a steady stream of viscous, incompressible fluid. The temperature of the cylinder is considered spatially uniform but not constant in time. The momentum and heat balance equations were solved numerically in elliptic coordinate system. The solutions span the parameter ranges 5 ? Re ? 40, 1 ? Pr ? 100 and axis ratio ε, 0.1 ? ε ? 0.75. The computations were focused on the influence of the axis ratio and volume heat capacity ratio on the heat transfer rate.     

Expedient Immobilization of TEMPO by Copper‐Catalyzed Azide‐Alkyne [3+2]‐Cycloaddition onto Polystyrene Resin

TEMPO was readily grafted by copper(I)‐catalyzed azide‐alkyne cycloaddition onto polystyrene. Starting with commercially available Merrifield resin (4.3 mmol/ g) almost quantitative loading of TEMPO onto the polymer was achieved (≥ 4 mmol/ g). The so obtained PS‐CLICK‐TEMPO allowed the oxidation of alcohols to aldehydes with bleach or molecular oxygen as the terminal oxidant with high yields and selectivity in multiple cycles without loss of activity.