Unprecedented Kinetic Inertness for a Mn2+‐Bispidine Chelate: A Novel Structural Entry for Mn2+‐Based Imaging Agents

The search for more biocompatible alternatives to Gd³⁺‐based MRI agents, and the interest in ⁵²Mn for PET imaging call for ligands that form inert Mn²⁺ chelates. Given the labile nature of Mn²⁺, high inertness is challenging to achieve. The strongly preorganized structure of the 2,4‐pyridyl‐disubstituted bispidol ligand L₁ endows its Mn²⁺ complex with exceptional kinetic inertness. Indeed, MnL₁ did not show any dissociation for 140 days in the presence of 50 equiv. of Zn²⁺ (37 °C, pH 6), while recently reported potential MRI agents MnPyC3A and MnPC2A‐EA have dissociation half‐lives of 0.285 h and 54.4 h under similar conditions. In addition, the relaxivity of MnL₁ (4.28 mm ^?1 s^?1 at 25 °C, 20 MHz) is remarkable for a monohydrated, small Mn²⁺ chelate. In vivo MRI experiments in mice and determination of the tissue Mn content evidence rapid renal clearance of MnL₁. Additionally, L₁ could be radiolabeled with ⁵²Mn and the complex revealed good stability in biological media.     

Production of metakaolin from industrial cellulose waste

Research focused on the transformation and utilization of industrial wastes into products of commercial interest plays an increasingly important role. Residual pulp can become useful in the manufacture of different materials, providing high value to this waste and reducing its environmental impact when disposed of improperly in the environment. The main constituents of this waste are kaolin and calcium carbonate (CaCO₃). Starting from kaolin, metakaolin can be produced by calcination of the residue at 630?°C for 2?h in a rotary reactor with air flow, followed by solubilization with hydrochloric acid to remove the CaCO₃. The development of technological alternatives aimed at the reuse of certain wastes can result in applications of real economic interest to the chemical industry and ceramics and glass, which is the case in this study. The raw material and metakaolin obtained were analyzed by thermogravimetric analysis and derivative thermogravimetric analysis, X-ray diffraction, and X-ray fluorescence spectroscopy with promising results. This is because metakaolin was obtained free of contamination by other materials.     

Conformational analysis: a new approach by means of chemometrics

In conformational analysis, the systematic search method completely maps the space but suffers from the combinatorial explosion problem because the number of conformations increases exponentially with the number of free rotation angles. This study introduces a new methodology of conformational analysis that controls the combinatorial explosion. It is based on a dimensional reduction of the system through the use of principal component analysis. The results are exactly the same as those obtained for the complete search but, in this case, the number of conformations increases only quadratically with the number of free rotation angles. The method is applied to a series of three drugs: omeprazole, pantoprazole, lansoprazole-benzimidazoles that suppress gastric-acid secretion by means of H+, K+-ATPase enzyme inhibition.     

Anisotropic Analysis of Some Gaussian Models

Although the classical Fractional Brownian Motion is often used to describe porosity, it is not adapted to anisotropic situations. In the present work, we study a class of Gaussian fields with stationary increments and spectral density. They present asymptotic self-similarity properties and are good candidates to model a homogeneous anisotropic material, or its radiographic images. Unfortunately, the paths of all Gaussian fields with stationary increments have the same apparent regularity in all directions (except at most one). Hence we propose here a procedure to recover anisotropy from one realization: computing averages over all the hyperplanes which are orthogonal to a fixed direction, we get a process whose Hölder regularity depends explicitly on the asymptotic behavior of the spectral density in this direction.     

Complete assignment of NMR data of 22 phenyl‐1H‐pyrazoles' derivatives

Complete assignment of ¹H and ¹³C NMR chemical shifts and J(¹H/¹H and ¹H/¹⁹F) coupling constants for 22 1‐phenyl‐1H‐pyrazoles' derivates were performed using the concerted application of ¹H 1D and ¹H, ¹³C 2D gs‐HSQC and gs‐HMBC experiments. All 1‐phenyl‐1H‐pyrazoles' derivatives were synthesized as described by Finar and co‐workers. The formylated 1‐phenyl‐1H‐pyrazoles' derivatives were performed under Duff's conditions. Copyright © 2011 John Wiley & Sons, Ltd.     

Evaluation of adaptive mesh refinement and coarsening for the computation of compressible flows on unstructured meshes

The compressible gas flows of interest to aerospace applications often involve situations where shock and expansion waves are present. Decreasing the characteristic dimension of the computational cells in the vicinity of shock waves improves the quality of the computed flows. This reduction in size may be accomplished by the use of mesh adaption procedures. In this paper an analysis is presented of an adaptive mesh scheme developed for an unstructured mesh finite volume upwind computer code. This scheme is tailored to refine or coarsen the computational mesh where gradients of the flow properties are respectively high or low. The refinement and coarsening procedures are applied to the classical gas dynamic problems of the stabilization of shock waves by solid bodies. In particular, situations where oblique shock waves interact with an expansion fan and where bow shocks arise around solid bodies are considered. The effectiveness of the scheme in reducing the computational time, while increasing the solution accuracy, is assessed. It is shown that the refinement procedure alone leads to a number of computational cells which is 20% larger than when alternate passes of refinement and coarsening are used. Accordingly, a reduction of computational time of the same order of magnitude is obtained. Copyright © 2005 John Wiley & Sons, Ltd.     

Heck reactions in monoglyme and diglyme using BmimCl as pre‐ligand

Heck reactions between iodobenzene and methyl acrylate were carried out in monoglyme and diglyme as solvents, using different ligands and palladium sources, and good to high yields were obtained in the production of (E)‐substituted olefins. The ionic liquid BmimCl was successfully utilized as pre‐ligand to substitute triphenylphosphine. Copyright © 2007 John Wiley & Sons, Ltd.     

Truncations of multilinear Hankel operators

We extend to multilinear Hankel operators the fact that some truncations of bounded Hankel operators are still bounded. We prove and use a continuity property of bilinear Hilbert transforms on products of Lipschitz spaces and Hardy spaces.

     

Addition of Surfactants and Non-Hydrolytic Proteins and Their Influence on Enzymatic Hydrolysis of Pretreated Sugarcane Bagasse

Poly(ethylene glycol) (PEG 4000) and bovine serum albumin (BSA) were investigated with the purpose of evaluating their influence on enzymatic hydrolysis of sugarcane bagasse. Effects of these supplements were assayed for different enzymatic cocktails (Trichoderma harzianum and Penicillium funiculosum) that acted on lignocellulosic material submitted to different pretreatment methods with varying solid (25 and 100 g/L) and protein (7.5 and 20 mg/g cellulose) loadings. The highest levels of glucose release were achieved using partially delignified cellulignin as substrate, along with the T. harzianum cocktail: increases of 14 and 18 % for 25 g/L solid loadings and of 33 and 43 % for 100 g/L solid loadings were reached for BSA and PEG supplementation, respectively. Addition of these supplements could maintain hydrolysis yield even for higher solid loadings, but for higher enzymatic cocktail protein loadings, increases in glucose release were not observed. Results indicate that synergism might occur among these additives and cellulase and xylanases. The use of these supplements, besides depending on factors such as pretreatment method of sugarcane bagasse, enzymatic cocktails composition, and solid and protein loadings, may not always lead to positive effects on the hydrolysis of lignocellulosic material, making it necessary further statistical studies, according to process conditions.     

Formation of catalytic silver nanoparticles supported on branched polyethyleneimine derivatives

A new and straightforward method for screening highly catalytically active silver nanoparticle-polymer composites derived from branched polyethyleneimine (PEI) is reported. The one-step systematic derivatization of the PEI scaffold with alkyl (butyl or octyl) and ethanolic groups led to a structural diversity correlated to the stabilization of silver nanoparticles and catalysis. Analysis of PEI derivative libraries identified a silver nanoparticle-polymer composite that was able to efficiently catalyze the p-nitrophenol reduction by NaBH(4) in water with a rate constant normalized to the surface area of the nanoparticles per unit volume (k(1)) of 0.57 s(-1) m(-2) L. Carried out in the presence of excess NaBH(4), the catalytic reaction was observed to follow pseudo-first-order kinetics and the apparent rate constant was linearly dependent on the total surface area of the silver nanoparticles (Ag-NPs), indicating that catalysis takes place on the surface of the nanoparticles. All reaction kinetics presented induction periods, which were dependent on the concentration of substrates, the total surface of the nanoparticles, and the polymer composition. All data indicated that this induction time is related to the resistance to substrate diffusion through the polymer support. Hydrophobic effects are also assumed to play an important role in the catalysis, through an increase in the local substrate concentration.