Ionic silica based hybrid material containing the pyridinium group used as an adsorbent for textile dye

The present study reports the development of an ionic silica based hybrid material containing the cationic pyridinium group, which was employed for the removal of the Reactive Red 194 textile dye from aqueous solution. Three hybrid material samples were prepared with planned textural and chemical properties, varying the inorganic precursor molar percentage in the sol-gel synthesis. The obtained samples were defined as Py/Si-90, Py/Si-92 and Py/Si-94, where the number specifies the inorganic molar percentage. The hybrid samples were characterized by elemental, infrared, (13)C and (29)Si NMR, N(2) adsorption-desorption isotherms and thermogravimetric analyses. The dye-removing ability of these adsorbents was determined by the batch contact adsorption procedure. Effects such as pH value and adsorbent dosage on the adsorption capacities were studied. Four kinetic models were applied. The adsorption was best fitted to Avrami fractional-order kinetic model for the three hybrid material samples. The kinetic data were also adjusted to an intra-particle diffusion model resulting three linear regions, indicating that the adsorption kinetics follows multiple sorption rates. The equilibrium data were fitted to Langmuir, Freundlich and Liu isotherm models. The maximum adsorption capacities were 165.4, 190.3 and 195.9 mg g(-1) for Py/Si-90, Py/Si-92 and Py/Si-94, respectively. Simulated dye-house effluents were used to check the applicability of the proposed adsorbents for effluent treatment. Dye loaded adsorbents were regenerated (>98.2%) by using 0.4 mol L(-1) of NaOH solution as an eluent.     

High Relaxivity Supramolecular Adducts Between Human‐Liver Fatty‐Acid‐Binding Protein and Amphiphilic GdIII Complexes: Structural Basis for the Design of Intracellular Targeting MRI Probes

Gadolinium complexes linked to an apolar fragment are known to be efficiently internalized into various cell types, including hepatocytes. Two lipid‐functionalized gadolinium chelates have been investigated for the targeting of the human liver fatty acid binding protein (hL‐FABP) as a means of increasing the sensitivity and specificity of intracellular‐directed MRI probes. hL‐FABP, the most abundant cytosolic lipid binding protein in hepatocytes, displays the ability to interact with multiple ligands involved in lipid signaling and is believed to be an obligate carrier to escort lipidic drugs across the cell. The interaction modes of a fatty acid and a bile acid based gadolinium complex with hL‐FABP have been characterized by relaxometric and NMR experiments in solution with close‐to‐physiological protein concentrations. We have introduced the analysis of paramagnetic‐induced protein NMR signal intensity changes as a quantitative tool for the determination of binding stoichiometry and of precise metal‐ion‐center positioning in protein–ligand supramolecular adducts. A few additional NMR‐derived restraints were then sufficient to locate the ligand molecules in the protein binding sites by using a rapid data‐driven docking method. Relaxometric and ¹³C NMR competition experiments with oleate and the gadolinium complexes revealed the formation of heterotypic adducts, which indicates that the amphiphilic compounds may co‐exist in the protein cavity with physiological ligands. The differences in adduct formation between fatty acid and bile acid based complexes provide the basis for an improved molecular design of intracellular targeted probes.     

High relaxivity supramolecular adducts between human-liver fatty-acid-binding protein and amphiphilic Gd(III) complexes: structural basis for the design of intracellular targeting MRI probes

Gadolinium complexes linked to an apolar fragment are known to be efficiently internalized into various cell types, including hepatocytes. Two lipid-functionalized gadolinium chelates have been investigated for the targeting of the human liver fatty acid binding protein (hL-FABP) as a means of increasing the sensitivity and specificity of intracellular-directed MRI probes. hL-FABP, the most abundant cytosolic lipid binding protein in hepatocytes, displays the ability to interact with multiple ligands involved in lipid signaling and is believed to be an obligate carrier to escort lipidic drugs across the cell. The interaction modes of a fatty acid and a bile acid based gadolinium complex with hL-FABP have been characterized by relaxometric and NMR experiments in solution with close-to-physiological protein concentrations. We have introduced the analysis of paramagnetic-induced protein NMR signal intensity changes as a quantitative tool for the determination of binding stoichiometry and of precise metal-ion-center positioning in protein-ligand supramolecular adducts. A few additional NMR-derived restraints were then sufficient to locate the ligand molecules in the protein binding sites by using a rapid data-driven docking method. Relaxometric and (13)C NMR competition experiments with oleate and the gadolinium complexes revealed the formation of heterotypic adducts, which indicates that the amphiphilic compounds may co-exist in the protein cavity with physiological ligands. The differences in adduct formation between fatty acid and bile acid based complexes provide the basis for an improved molecular design of intracellular targeted probes.     

Activity of Spray-dried Microparticles Containing Pomegranate Peel Extract against <em>Candida albicans</em>

Pomegranate has attracted interest from researchers because of its chemical composition and biological properties. It possesses strong antioxidant activity, with potential health benefits, and also antimicrobial properties. The aim of this study was to produce microparticles containing pomegranate extract by the spray-drying technique, utilizing alginate or chitosan as encapsulating agents. Characterization and antifungal assays were carried out. Production yields were about 40% for alginate microparticles and 41% for chitosan. Mean diameters were 2.45 μm and 2.80 μm, and encapsulation efficiencies were 81.9% and 74.7% for alginate and chitosan microparticles, respectively. The spray-drying process preserved the antifungal activity against Candida albicans. These results could be useful for developing dosage forms for treating candidiasis, and should be further investigated in in vivo models.     

Improved syntheses of bis(beta-cyclodextrin) derivatives, new carriers for gadolinium complexes

In the last decade a number of reports have been published on the synthesis and characterization of bridged cyclodextrin dimers (bis-CDs) connected with linkers of different lengths and structures. These dimers, having two hydrophobic cavities in close proximity, display much higher binding affinities and molecular selectivities than parent CDs, forming stable supramolecular adducts. We describe new synthetic protocols for the preparation of bis(beta-CDs) bearing 2-2', 3-3' and 6-6' bridges. Some of the critical steps were carried out either under high-intensity ultrasound (US) or microwave (MW) irradiation. Bis(beta-CDs) containing 6-6' ureido- and thioureido-bridges were prepared in high yields by a MW-promoted aza-Wittig reaction using polymer-bound triphenylphosphine, while those containing 2,2' and 3,3' bridges were prepared from mono-alkenyl beta-CDs by the cross-metathesis reaction (homodimerization) in the presence of 2(nd)-generation Grubbs catalyst under sonochemical conditions. By these improved protocols CD dimers could be obtained in gram amounts to prepare stable adducts of bis-CDs with contrast agents (CAs) containing gadolinium(iii) chelates. In the case of Gd(iii) chleate "G-1" the inclusion complexes were found to be 2 to 3 orders of magnitude more stable than that formed by beta-CD (K(ass) = 4.3 x 10(4) M(-1)vs 8.0 x 10(2) M(-1)). Relaxivity increased as well by factors of 3 and 4, viz. from 9.1 mM(-1) s(-1) (beta-CD) to 27.7 and 35 mM(-1) s(-1).     

Magnetic properties of iron loaded MCM-48 molecular sieves

Mesoporous molecular sieves of MCM-48 type were loaded with iron by the wet impregnation method, using Fe(III) nitrate or Fe(II) sulfate aqueous solutions as Fe sources, to obtain a magnetic porous composite. The iron loaded materials were characterized by XRD, N₂ adsorption and DRUV-vis and compared with the Si-MCM-48 host. Their magnetic properties were studied by measuring the hysteresis loops up to 1.5 T at different temperatures (5-300 K) and by magnetization vs. temperature curves following the conventional zero field cooling (ZFC) and field cooling (FC) protocols. Materials with high structure regularity and surface area are obtained, which exhibit a mixed paramagnetic and superparamagnetic behavior, arising in isolated iron ions inserted in the host framework, and in small iron oxide clusters or nanoparticles forming inside the pores, respectively. Larger hematite particles (8-13 nm) grown on the external surface provide a quite small ferromagnetic contribution to the hysteresis loop.     

Experimental and theoretical structure and vibrational analysis of ethyl trifluoroacetate,CF3CO2CH2CH3

The molecular structure and conformational properties of ethyl trifluoroacetate, CF₃CO₂CH₂CH₃, were determined in the gas phase by electron diffraction, and vibrational spectroscopy (IR and Raman). The experimental investigations were supplemented by ab initio (MP2) and DFT quantum chemical calculations at different levels of theory. Experimental and theoretical methods result in two structures with C_s (anti–anti) and C₁ (anti–gauche) symmetries, the former being slightly more stable than the latter. The electron‐diffraction data are best fitted with a mixture of 56% anti–gauche and 44% anti–anti conformers. The conformational preference was also studied using the total energy scheme, and the natural bond orbital scheme. Also, the infrared spectra of CF₃CO₂CH₂CH₃ are reported for the gas, liquid and solid states, as is the Raman spectrum of the liquid. The comparison of experimental averaged IR spectra of C_s and C₁ conformers provides evidence for the predicted conformations in the IR spectra. Harmonic vibrational wavenumbers and scaled force fields have been calculated for both conformers. Copyright © 2009 John Wiley & Sons, Ltd.     

A basis for the non-crossing partition lattice top homology

We find a basis for the top homology of the non-crossing partition lattice T _n . Though T _n is not a geometric lattice, we are able to adapt techniques of Björner (A. Björner, On the homology of geometric lattices. Algebra Universalis 14 (1982), no. 1, 107–128) to find a basis with C _n?1 elements that are in bijection with binary trees. Then we analyze the action of the dihedral group on this basis.     

Ionic silsesquioxane film immobilized on silica applied in the development of carbon paste electrode for determination of methyl parathion

A mesoporous silica-based hybrid material composed of silica xerogel modified with an ionic silsesquioxane, which contains the 1,4-diazoniabicyclo[2.2.2]octane chloride group, was obtained. The silsesquioxane film is highly dispersed on the surface. This hybrid material was utilized to develop a carbon paste electrode (CPE) for determination of methyl parathion. Transmission FTIR, elemental analysis and N₂ adsorption–desorption isotherms were used for characterization of the material. The electrochemical behavior of methyl parathion was evaluated by cyclic voltammetry and differential pulse voltammetry. It was observed a linear response to methyl parathion in the concentration range from 1.25 × 10^?7 to 2.56 × 10^?6 mol L^?1 by employing the carbon paste electrode, in Britton–Robinson buffer solution (pH 6). The achieved detection limit (3 SD of the blank divided by the slope of calibration curve) was 0.013 µmol L^?1 and sensitivity was 6.3 µA µmol L^?1. This result shows the potentiality of this electrode for application as electrochemical sensor for methyl parathion.     

Temporal decay of the catalytic oxidation of methane over palladium supported on silica

The temporal decay of the oxidation of methane(CH4-O2reaction)over palladium supported on silica is determined experimentally at different temperatures,comparing the results with those of various classical models which show the behavior of the adsorbed phase as the cause of the phenomenon.This effect is visualized through Monte Carlo simulations of the CH4-O2reaction on a mixed lattice whose partial poisoning,due to the configuration of the OH groups on the surface of the adsorbate,is translated into a gradual decay of the reaction’s activity.