A categorization method applied to the study of urban road traffic noise

The present work summarizes a study of the hypothesis that urban noise can be stratified by measuring street noise according to a prior classification of a town's streets according to their use in communicating the different zones of the town. The method was applied to five medium-sized Spanish towns (Vitoria-Gasteiz, Salamanca, Badajoz, Cáceres, and Mérida) with populations ranging from 218 000 down to 50000 and with different socio-economic characteristics, climate, etc. As the initial hypothesis of the work was that traffic is the main source of urban noise and is also the principal cause of the variability of the sound levels measured in urban settings, the study focused only on the five nonpedestrian categories of streets. The continuous equivalent sound level (Leq) was employed in the statistical analysis as it is commonly used as a general noise index, and other noise indicators such as L(DN) or L(DEN) are calculated from it. It was found that, although differences between the medians were not statistically significant in some of the towns for certain pairs of adjacent categories, the differences between pairs of nonadjacent categories were always significant, indicative of the stratification of noise in these five towns. Further studies on other medium-sized towns and on large towns and small villages would be needed to test whether the present definition of street categories is extensible elsewhere without modification.     

A simple validated RP‐HPLC bioanalytical method for the quantitative determination of a novel valproic acid arylamide derivative in rat hepatic microsomes

A simple and specific bioanalytical method based on reversed‐phase high‐performance liquid chromatography (RP‐HPLC) coupled with ultraviolet detection was developed and validated for the determination of a novel valproic acid arylamide, N‐(2‐hydroxyphenyl)‐2‐propylpentanamide (HO‐AAVPA) in rat hepatic microsomes (a subcellular fraction containing phase I enzymes, especially cytochrome P450). The chromatographic separation was achieved using a reversed‐phase Zorbax SB‐C₁₈ column and a mobile phase of acetic acid in water (0.2% v/v) and acetonitrile (40:60 v/v) with a flow rate of 0.5 mL/min. The calibration curve was linear over the range of 882–7060 ng/mL (r² = 0.9987), and the lower limit of quantification and the lower limit of determination were found to be 882 and 127.99 ng/mL, respectively. The method was validated with excellent sensitivity, and intra‐day accuracy and precision varied from 93.79 to 93.12%, and from 2.12 to 4.36%, respectively. The inter‐day accuracy and precision ranged from 93.29 to 97.30% and from 0.68 to 3.60%, respectively. The recovery of HO‐AAVPA was measured between 91.36 and 97.98%. The assay was successfully applied to the analysis of kinetic metabolism and pharmacokinetic parameters in vitro by a substrate depletion approach. Copyright © 2014 John Wiley & Sons, Ltd.     

Quantitative measurement of solids distribution in gas–solid riser flows using electrical impedance tomography and gamma densitometry tomography

An electrical impedance tomography (EIT) system has been developed to non-invasively measure particle distributions in the riser of a pilot-scale circulating fluidized bed (CFB). Although EIT systems have often been applied to yield qualitative information about gas–solid flows, the present EIT system yields quantitative information that is validated by comparison to a gamma densitometry tomography (GDT) system. EIT and GDT were applied to the CFB riser (14-cm inner diameter, 5.77-m height) containing fluid catalytic cracking particles in air. The flows examined were annular with a dilute core and had average and near-wall solids volume fractions up to 0.25 and 0.66, respectively. For all cases, the average and near-wall solids volume fractions from EIT and GDT agreed to within 0.03 and 0.07, respectively. This good agreement suggests that, where feasible, EIT can be used in place of GDT, which is advantageous since EIT systems are often safer, less expensive, and faster than GDT systems.     

Polycaprolactone membranes reinforced by toughened sol–gel produced silica networks

The aim of this work is to develop polycaprolactone based porous materials with improved mechanical performance to be used in bone repair. The hybrid membranes consist in a polymeric porous material in which the pore walls are coated by a silica thin layer. Silica coating increases membrane stiffness with respect to pure polymer but in addition filling the pores of the polymer with a silica phase improves bioactivity due to the delivery of silica ions in the neighborhood of the material in vivo. Nevertheless silica network, even that produced by sol–gel, might be too stiff and brittle what is not desirable for its performance as a coating. In this work we produced a toughened silica coating adding chitosan and 3-glycidoxypropyltrimethoxysilane (GPTMS) to the precursor solution looking for having polymer chains linked by covalent bonding to the silica network. Hybrid polymer–silica coating was produced by in situ sol–gel reaction using Tetraethyl orthosilicate (TEOS), GPTMS and chitosan. Chemical reaction between amine groups of chitosan chains and epoxy groups of GPTMS allowed covalent bonding of polymer chains to the silica network. Physical properties of the hybrid membranes were characterized and cell attachment of MC3T3-E1 pre-osteoblastic cells on the surface of these supports was assessed.     

Divergent Pathways and Competitive Mechanisms of Metathesis Reactions between 3‐Arylprop‐2‐ynyl Esters and Aldehydes: An Experimental and Theoretical Study

Mechanistic studies of the reaction between 3‐arylprop‐2‐ynyl esters and aldehydes catalyzed by BF₃ ? Et₂O were performed by isotopic labeling experiments and quantum chemical calculations. The reactions are shown to proceed by either a classical alkyne–carbonyl metathesis route or an unprecedented addition–rearrangement cascade. Depending on the structure of the starting materials and the reaction conditions, the products of these reactions can be Morita–Baylis–Hillman (MBH) adducts that are unavailable by traditional MBH reactions or E‐ and Z‐α,β‐unsaturated ketones. ¹⁸O‐Labeling studies suggested the existence of two different reaction pathways to the products. These pathways were further examined by quantum chemical calculations that employed the DFT(wB97XD)/6‐311+G(2d,p) method, together with the conductor‐like screening model for realistic solvation (COSMO‐RS). By using the wB97XD functional, the accuracy of the computed data is estimated to be 1–2 kcal mol^?1, shown by the careful benchmarking of various DFT functionals against coupled cluster calculations at the CCSD(T)/aug‐cc‐pVTZ level of theory. Indeed, most of the experimental data were reproduced and explained by theory and it was convincingly shown that the branching point between the two distinct mechanisms is the formation of the first intermediate on the reaction pathway: either the four‐membered oxete or the six‐membered zwitterion. The deep mechanistic understanding of these reactions opens new synthetic avenues to chemically and biologically important α,β‐unsaturated ketones.     

Dynamical features of the solid motion in gas–solid risers

The trajectories of a solid tracer with the same characteristics as the circulating solids in the risers of two pilot-scale circulating fluidized beds (CFBs), obtained by the computer automated radioactive particle tracking (CARPT) technique, are examined in detail to get further insights into the complex solids dynamics of these systems. The analysis uses tools from the theory of non-linear dynamics and symbolic dynamics. Distinct features of the solids dynamics within the fast fluidization and the dilute phase transport flow regimes are highlighted and related to the operating conditions. The possibility of downflow cluster existence within the central region of the riser is particularly examined.     

Brønsted acid site number evaluation using isopropylamine decomposition on Y-zeolite contaminated with vanadium in a simultaneous DSC–TGA analyzer

Acid-site catalyzed decomposition of isopropylamine was followed in a simultaneous DSC–TGA analyzer. USY zeolite samples with and without vanadium were studied. Results show that acid sites number decreases linearly with vanadium concentration in zeolite indicating that vanadium neutralizes acid sites on catalyst and the metal is able to move on the surface of the solid. The neutralizing species probably contain only one vanadium atom. The reaction enthalpy plus desorption heat of the products show that vanadium preferentially neutralizes the strongest acid sites on the zeolite. The application of the simultaneous DSC–TGA technique to quantify Brønsted acid sites on solids by this reaction is novel.     

Why Are Selenouracils as Basic as but Stronger Acids than Uracil in the Gas Phase?

The gas‐phase basicity and acidity of 2‐selenouracil ( 2SU ), 4‐selenouracil ( 4SU ), and 2,4‐diselenouracil ( 24SU ) have been calculated at the B3LYP/6‐311+G(3df,2p) level of theory. Our results showed that all these compounds behave as bases of moderate strength in the gas phase. As was found for uracil and for the thiouracil analogues, the most basic site is the heteroatom at position 4, and only for 2SU is there a certain ambiguity in assigning the basic site. More importantly, with the only exception of 2SU , selenouracils are as basic as or slightly less basic than uracil, because the replacement of the oxygen atom at position 2 by a selenium atom leads to an increase of the electron delocalization inside the six‐membered ring, which decreases the intrinsic basicity of the heteroatom at position 4. As already reported for uracil and thiouracils, for selenouracils N1 is the most acidic site. However, selenouracils are predicted to be stronger acids than uracil. This acidity enhancement is essentially due to a specific stabilization of the anion when O is replaced by Se. Two factors are responsible for this stabilization: a significant aromatization of the ring upon deprotonation and a better dispersion of the excess electron density when the system contains third‐row atoms.