Synthesis and structure determination of a new microporous zeolite with large cavities connected by small pores

A new small-pore germanosilicate zeolite, named as ITQ-49, has been synthesized using a new ditetraalkylphosphonium dication as an organic structure-directing agent, and its structure has been solved by direct methods applied to the powder X-ray diffraction pattern of the calcined solid. This new zeolite crystallizes in the space group Immm with cell parameters a = 19.6007(8) ?, b = 18.3274(7) ?, and c = 16.5335(6) ?. The pore topology of ITQ-49 consists of large, nonspherical cavities that are connected to each other through small eight-membered-ring windows, resulting in a unidirectional small-pore zeolite that has a relatively large adsorption capacity. Also, ITQ-49 contains double four-membered-ring units where Ge is preferentially located, and fluoride anions are placed inside these units.     

Role of anisotropy in electrodynamically induced colloidal aggregates

We investigate the assembly of spherical and anisotropic colloidal particles with the shape of peanuts when subjected to an external alternating electric field. By varying the strength and frequency of the applied field, we observe that both types of particles form clusters at low frequencies due to attractive electrohydrodynamic interactions or disperse into a liquidlike phase at high frequencies due to repulsive dipolar interactions. We characterize the observed structures via pair correlation functions and radius of gyration, and observe a clear difference in the ordering process between the isotropic and anisotropic colloids. Further on, we interpret the cluster formation kinetics in terms of dynamic scaling theory, and observe a faster aggregation of the anisotropic colloids with respect to the isotropic ones.     

Pluriharmonic mappings and linearly connected domains in ℂ n

In this paper we obtain certain sufficient conditions for the univalence of pluriharmonic mappings defined in the unit ball \(\mathbb{B}^n \) of ? ⁿ . The results are generalizations of conditions of Chuaqui and Hernández that relate the univalence of planar harmonic mappings with linearly connected domains, and show how such domains can play a role in questions regarding injectivity in higher dimensions. In addition, we extend recent work of Hernández and Martín on a shear type construction for planar harmonic mappings, by adapting the concept of stable univalence to pluriharmonic mappings of the unit ball \(\mathbb{B}^n \) into ? ⁿ .     

Benzylic coupling constants in toluene derivatives by J doubling in the frequency domain and DFT calculations

The recently modified J doubling in the frequency domain method (MJDFDM) allowed the determination of ^{4, 5, 6}J in toluene, a series of 4‐mono‐ and 3,5‐disubstituted toluene derivatives, as well as in 4‐picoline. The methyl and aromatic signals were subjected to successive deconvolution processes, which at the end led to singlet signals and afforded the corresponding coupling constant values with a high degree of accuracy. Density functional theory calculation of benzylic coupling constants by addition of the Fermi contact, the spin‐dipole, the diamagnetic spin‐orbit, and the paramagnetic spin‐orbit terms revealed good agreement between predicted and measured values when the B3LYP/aug‐cc‐pVTZ level of theory was used. Evaluation of the substituent effect over the coupling constant was made for all studied compounds and some limitations of the methodology were evidenced. Copyright © 2009 John Wiley & Sons, Ltd.     

Enhancement of cyanide photocatalytic degradation using sol–gel ZnO sensitized with cobalt phthalocyanine

In this work, the photodegradation of cyanide in aqueous suspension was used to determine the photocatalytic activity of sol–gel prepared ZnO which was impregnated with the Co (II) phthalocyanine (CoPc), as sensitizer. The prepared catalyst was characterized by Scanning Electron Microscopy (SEM) with Energy Dispersed Spectroscopy (EDS) detector, X-Ray Diffraction (XRD), Fourier Transform Infrared spectroscopy (FT-IR) and Diffuse UV–Vis Reflectance spectroscopy. Specific surface area was calculated from nitrogen adsorption isotherm using BET method. Compared with commercial ZnO and TiO₂ Degussa P25 photocatalysts, the sol–gel prepared ZnO catalyst sensitized with cobalt phthalocyanine showed the highest activities for degradation of cyanide in aqueous solution under visible light irradiation.     

Determination of 5-nitroimidazoles and metabolites in environmental samples by micellar electrokinetic chromatography

A method based on micellar electrokinetic chromatography (MEKC) with UV detection has been developed for the determination of nine 5-nitroimidazoles (5-NDZs), including metabolites in river water samples. Due to the relative insensitivity of UV detection in MEKC, a solid-phase extraction (SPE) method has been proposed that preconcentrates water samples fiftyfold and cleans them up off-line. An on-line preconcentration approach based on sweeping and the use of an extended light path fused-silica capillary (64.5?cm?×?50?μm i.d., 56?cm effective length) was also found to improve the sensitivity of the method. Separation was carried out in <21?min using 20?mM phosphate buffer (pH 6.5) and 150?mM SDS as the background electrolyte (BGE). The temperature of the capillary was kept constant at 20°C, a voltage of 25?kV was applied (normal mode), and a detected wavelength of 320?nm was utilized. Hydrodynamic injection (50?mbar for 15?s) of the samples, which were dissolved in 20?mM phosphate (pH 6.5), was employed. The limits of detection were lower than 1.1?μg?L(-1). Recoveries of >80% from spiked river water samples were obtained for most of the analytes at three different concentration levels with acceptable precision. This method could provide an efficient and economical alternative to the use of chromatographic methods to monitor nitroimidazole residues, thus supplementing the relatively few methods available for the analysis of these compounds in environmental samples.     

LaTiO2N/In2O3 photoanodes with improved performance for solar water splitting

LaTiO(2)N photoanodes for solar water splitting were prepared by electrophoretic deposition and demonstrated the best photocurrents ever reported for this material. Further important enhancement of the performance was obtained by the use of a sputtered In(2)O(3) overlayer.     

Solvent-solvent and solvent-solute interactions in a 3D chloroform clathrate with diorganotin macrocycles in the nano-sized pores

A 3D clathrate of deuterochloroform molecules was formed in the presence of nano-sized macrocyclic molecules.     

Ring Puckering in Chloride-[N,N′-Bis(2,6-Diisopropylphenyl)-2,2,6,6-Tetramethylheptane-3,5-Diiminato]Tin(II)

Abstract  

Reaction of the β-diketiminato lithium salt {CH[(C^tBu)(2,6-ⁱPr₂C₆H₃N)]₂}⁻Li⁺ with SnCl₂ provided the derivative {CH[(C^tBu)(2,6-ⁱPr₂C₆H₃N)₂}SnCl with a three-coordinate tin(II) ion. The crystal structure shows a non-planar ligand skeleton and a tin(II) ion with a distorted tetrahedral pyramidal geometry with one vertex occupied by an unshared electron pair. The Sn(II) ion out of the N2–C3–C2–C1–N1 plane (Φ-length) is 0.674 ? because of the steric hindrance between the tert-butyl groups and the N-aryl groups. The Sn–N1 [2.224 (19) ?] and Sn–N2 [2.1423 (18) ?] distances in the heterocycle corresponded with a delocalized system, while the most acute angle was associated with the bite of the chelating ligand N–Sn–N 87.94 (7)°.     

Study of the thermal degradation of bioactive sol–gel coatings for the optimization of its curing process

A set of materials has been prepared by sol–gel process containing different quantities of hydroxyapatite (0, 2.5 and 5% HAp w/w) using as silica precursors glycidyloxypropyltrimethoxysilane (GPTMS) and triethoxyvinylsilane (VTES). In order to optimize the curing process to obtain sintherized systems (inorganic network) or hybrid systems (organic–inorganic) a TG and FTIR studies have been developed and degradation kinetic triplet parameters were obtained (the activation energy, pre-exponential factor, and function of degree of conversion). The kinetic study was analyzed by means of an integral isoconversional non-isothermal procedure (model free), and the kinetic model was determined by the Coats–Redfern method and through the compensation effect (IKR). All the systems followed the n = 6 kinetic model. The addition of HAp increases the thermal stability of the systems. The isothermal degradation was simulated from non-isothermal data, and the curing process could be defined to obtain the two types of materials. Temperature under 250 °C allows the formation of hybrids networks.