B‐MWW Zeolite: The Case Against Single‐Site Catalysis

Boron‐containing materials have recently been identified as highly selective catalysts for the oxidative dehydrogenation (ODH) of alkanes to olefins. It has previously been demonstrated by several spectroscopic characterization techniques that the surface of these boron‐containing ODH catalysts oxidize and hydrolyze under reaction conditions, forming an amorphous B₂(OH)_xO_(3?x/2) (x=0–6) layer. Yet, the precise nature of the active site(s) remains elusive. In this Communication, we provide a detailed characterization of zeolite MCM‐22 isomorphously substituted with boron (B‐MWW). Using ¹¹B solid‐state NMR spectroscopy, we show that the majority of boron species in B‐MWW exist as isolated BO₃ units, fully incorporated into the zeolite framework. However, this material shows no catalytic activity for ODH of propane to propene. The catalytic inactivity of B‐MWW for ODH of propane falsifies the hypothesis that site‐isolated BO₃ units are the active site in boron‐based catalysts. This observation is at odds with other traditionally studied catalysts like vanadium‐based catalysts and provides an important piece of the mechanistic puzzle.     

Aqueous extracts of Agave sisalana boles have prebiotic potential

Abstract

This work aimed at evaluating the prebiotic potential of the aqueous extract and crude polysaccharides from Agave sisalana boles by an in vitro screening. Crude polysaccharides were obtained from the aqueous bole extract by precipitation with acetone and resuspension in water. The liquid extract and the polysaccharide solution were then spray dried and submitted to thermal analysis and quantification of metabolites. Prebiotic activity was checked on probiotic strains belonging to the Lactobacillus genus using inulin, fructo-oligosaccharides, fructose and glucose as positive controls. The powder of A. sisalana bole extract, which has recently been identified as a rich source of inulin, exhibited higher potential of fermentation compared with crude polysaccharides.     

Modified electrode with reduced graphene oxide/poly(3-hydroxyphenylacetic acid): a new platform for oligonucleotide hybridization

Journal of Solid State Electrochemistry - This paper reports a new platform for oligonucleotide hybridization, prepared by electropolymerization of 3-hydroxyphenylacetic acid onto gold electrode...     

Dependence of collision‐induced dissociation energy on molecular degrees of freedom as a means to assess relative binding affinity in multivalent complexes

In collision‐induced dissociation mass spectrometry experiments, the collision energy required for dissociation linearly depends on the degrees of freedom in the precursor ion. The magnitude of the slope of this relationship previously has been shown to qualitatively correlate to the relative binding strength of a noncovalently bound, monovalent complex. The goal of the work presented here is to determine if a similar methodology can be applied for assessing relative binding strengths in multivalent species. We have tested the method on complexes formed from 18‐crown‐6 and a variety of protonated, primary alkylamines, [C_nH_2n+1NH₃]⁺ (n = 9, 12, 14, 16 and 18) and alkyldiamines, [H₃NC_nH_2nNH₃]²⁺ (n = 3, 5, 6, 9 and 12), and compared our results with dissociation energies calculated using density functional theory at the B3LYP/6‐31G* level. We found that the method correctly assessed the stronger crown ether/headgroup interaction in the two divalent species (1:1 and 2:1 complexes formed from the diaminoalkanes) compared with the weaker interaction in the monovalent species (1:1 complexes formed from mono‐aminoalkanes). However, the experimental method could not distinguish between the binding strengths of the two divalent complexes, perhaps because their calculated dissociation energies were quite similar. Our preliminary results suggest that this method could potentially be used for a quick and simple analysis of binding strengths in multivalent species if the binding strengths of the species are significantly different from one another. Copyright © 2011 John Wiley & Sons, Ltd.     

Experimental and theoretical analysis of bias ionization by?α-particles in a nitrogen laser

Nitrogen laser performance with TE configuration and wedge electrodes is analyzed with background ionization in the laser discharge channel by α particles at a low exposition rate. With the bias ionization, the laser power presents two peaks as a function of gas pressure, with one at the normal low pressure, without bias ionization, and the other at high pressure generated by bias ionization. A simple theoretical model has been developed in a trial to understand this behavior. This model was first tested in later results for a TE configuration nitrogen laser, with flat electrodes, without and with bias ionization. It has been observed that due to the competition between electrode shielding by positively charged α particles and bulk ionization by impact, the laser energy is suppressed with pressure below 50 Torr and enhanced above it.     

Structural deformation monitored by vibrational properties and orbital modeling in (Pb,Sm)TiO3 systems

Pb_1−xSm_xTiO₃ (PST) powders with x varying from 0 to 0.1 were obtained by the polymeric precursor method, a soft chemical route. The vibrational properties relating tetragonal to pseudo-cubic phase transition were studied by Raman spectroscopy. The results obtained showed that the phase transition is extremely dependent upon the samarium content and presents a diffuse behavior. Monitoring of the oxygen 2p and titanium 3d orbitals was performed by the periodic mechanical quantum method, revealing the changes that occur with the distribution and contribution of the hybrid orbitals due to the samarium influence.     

Li‐doped nanosized TiO2 powder with enhanced photocalatylic acivity under sunlight irradiation

This work reports on the synthesis of Li‐doped TiO₂ nanoparticles using the sol–gel process and solid‐state sintering, and investigates their potential use as a photocatalyst for degradation under sunlight excitation of different organic model compounds in aqueous solution. The structure of the nanocrystals was examined by X‐ray diffraction, UV‐vis ground state diffuse reflectance absorption spectra and X‐ray photoelectron emission spectroscopy. Results showed that samples prepared by sol–gel process and calcined at 400 °C are composed of a mixture of anatase and rutile phases, in contrast to the one prepared by solid‐state sintering, which exhibits an anatase phase with Li being involved in a spinel phase. The photocatalytic degradation of aqueous solutions of different aromatic compounds was successfully achieved under sunlight excitation in presence of Li‐doped TiO₂ prepared via sol–gel process. It was shown that the calcination temperature and the preparation mode greatly affect the photocatalytic efficiency. Copyright © 2010 John Wiley & Sons, Ltd.     

The bicyclic n,n'-diacylaminal: a new motif for molecular self-assembly

A cage-shaped N,N'-diacylaminal crystallizes from some aromatic solvents as "supramolecular chair cyclohexanes", squat cylindrical hexamers with approximate D3d symmetry containing two arene molecules, and from other aromatic and nonaromatic solvents as infinite tapes. A homologous diacylaminal crystallizes only as an infinite tape. The hexamers represent the first examples of cyclic hexamers held together by %@mt;sys@%%@bold@%R%@rsf@%%@sx@%2%@be@%2%@sxx@%%@fn;(;vis;full;auto@%8%@fnx;);vis;full@%-type%@mx@% hydrogen bonds in which the hydrogen-bonded atoms are not coplanar. The diacylaminal represents a new supramolecular synthon, one perhaps more suited to the design of three-dimensional architectures.