Determination of amylose content in starch using Raman spectroscopy and multivariate calibration analysis

Fourier transform Raman spectroscopy and chemometric tools have been used for exploratory analysis of pure corn and cassava starch samples and mixtures of both starches, as well as for the quantification of amylose content in corn and cassava starch samples. The exploratory analysis using principal component analysis shows that two natural groups of similar samples can be obtained, according to the amylose content, and consequently the botanical origins. The Raman band at 480 cm^?1, assigned to the ring vibration of starches, has the major contribution to the separation of the corn and cassava starch samples. This region was used as a marker to identify the presence of starch in different samples, as well as to characterize amylose and amylopectin. Two calibration models were developed based on partial least squares regression involving pure corn and cassava, and a third model with both starch samples was also built; the results were compared with the results of the standard colorimetric method. The samples were separated into two groups of calibration and validation by employing the Kennard-Stone algorithm and the optimum number of latent variables was chosen by the root mean square error of cross-validation obtained from the calibration set by internal validation (leave one out). The performance of each model was evaluated by the root mean square errors of calibration and prediction, and the results obtained indicate that Fourier transform Raman spectroscopy can be used for rapid determination of apparent amylose in starch samples with prediction errors similar to those of the standard method.

On the relationships between molecular conformations and intermolecular contacts toward crystal self-assembly of mono-, di-, tri-, and tetra-oxygenated xanthone derivatives

Oxygenated xanthones have been extensively investigated over the years, but there are few reports concerning their crystal structure. Our chemical investigations of Brazilian plants resulted in the isolation of four natural products named 1-hydroxyxanthone (I), 1-hydroxy-7-methoxyxanthone (II), 1,5-dihydroxy-3-methoxyxanthone (III), and 1,7-dihydroxy-3,8-dimethoxyxanthone (IV). The structures of these compounds were established on the basis of single crystal X-ray diffraction. The xanthone nucleus conformation is essentially planar with the substituents adopting the orientations less sterically hindered. In addition, classical intermolecular hydrogen bonds (O–H···O) present in III and IV give rise to infinite ribbons. However, the xanthone I does not present any intermolecular hydrogen bonds, meanwhile the xanthone II presents only a non-classical one (C–H···O). The crystal packing of all xanthone structures is also stabilized by π–π interactions. The fingerprint plots, derived from the Hirshfeld surfaces, exhibited significant features of each crystal structures.     

Morphology and protein content of hepatocytes in type I diabetic rats submitted to physical exercises

The importance of physical exercise practice in the treatment of diabetes has been reported in many studies recently, but only limited data can be found regarding its benefits on liver morphology and protein content of hepatocytes. In order to assess the changes arising from the development of type I diabetes and the benefits of a training protocol, Wistar rats were divided into four groups: sedentary control (SC), trained control (TC), sedentary diabetic (SD) and trained diabetic (TD). The training protocol consisted of swimming for 60 min a day, 5 days/week, during 8 weeks. Liver samples were collected, processed and analyzed by histochemical and ultrastructural techniques. Biochemical tests were also conducted to examine the protein content and quantity of DNA in the liver. In morphological assessment, the presence of areas of cytoplasmic basophilia observed in control subjects was not visualized in sedentary diabetics. It was related to differences in the amount of mitochondria in the cytosol. The mitochondrial structure has not undergone relevant changes, and the number of rough endoplasmic reticulum cisterns was clearly inferior in sedentary diabetics, suggesting lower protein production. However, the biochemical analysis of protein content indicated no statistical differences between groups. The exercise, in turn, was not responsible for major changes in these characteristics. On the whole, the morphological damages arising from type I diabetes were noteworthy. Nevertheless, regular physical training was not responsible for significant improvements in some respects, making evident the need for combined application of a distinct form of treatment.     

Simultaneous velocity and temperature measurements in gaseous flow fields using the VENOM technique

We present an initial demonstration of simultaneous velocity and temperature mapping in gaseous flow fields using a new nitric oxide planar laser-induced fluorescence-based method. The vibrationally excited NO monitoring (VENOM) technique is an extension of two-component velocimetry using vibrationally excited NO generated from the photodissociation of seeded NO(2) [Appl. Opt. 48, 4414 (2009)], where the two sequential fluorescence images are obtained probing two different rotational states to provide both velocity and temperature maps. Comparisons to computational fluid dynamics simulations show that the initial VENOM measurements provide good velocity and temperature maps in the relatively high-density regions of the flow, where the rms uncertainties are approximately 5% for velocity and 9% for temperature.     

Asymptotic stability for Bresse systems

In this paper consider a vibrating system of Bresse type in a one-dimensional bounded domain with a nonlinear damping acting in the equation of the shear angle displacement, and nonlinear localized damping in other equations. We show the asymptotic stability without imposing conditions about the equal-speed wave propagation, using a method developed by Lasiecka and Tataru [9].     

A finite element formulation satisfying the discrete geometric conservation law based on averaged Jacobians

In this article, a new methodology for developing discrete geometric conservation law (DGCL) compliant formulations is presented. It is carried out in the context of the finite element method for general advective–diffusive systems on moving domains using an ALE scheme. There is an extensive literature about the impact of DGCL compliance on the stability and precision of time integration methods. In those articles, it has been proved that satisfying the DGCL is a necessary and sufficient condition for any ALE scheme to maintain on moving grids the nonlinear stability properties of its fixed‐grid counterpart. However, only a few works proposed a methodology for obtaining a compliant scheme. In this work, a DGCL compliant scheme based on an averaged ALE Jacobians formulation is obtained. This new formulation is applied to the θ family of time integration methods. In addition, an extension to the three‐point backward difference formula is given. With the aim to validate the averaged ALE Jacobians formulation, a set of numerical tests are performed. These tests include 2D and 3D diffusion problems with different mesh movements and the 2D compressible Navier–Stokes equations. Copyright © 2011 John Wiley & Sons, Ltd.     

Fujita type exponent for fully nonlinear parabolic equations and existence results

In this paper, we prove that a class of parabolic equations involving a second order fully nonlinear uniformly elliptic operator has a Fujita type exponent. These exponents are related with an eigenvalue problem in all RN and play the same role in blow-up theorems as the classical p^?=1+2/N introduced by Fujita for the Laplacian. We also obtain some associated existence results.     

A straightforward synthesis of pyrimido[4,5-b]quinoline derivatives assisted by microwave irradiation

Several pyrimido[4,5-b]quinolines, flavin analogues, have been prepared by assisted microwave intramolecular cyclization of N⁴-substituted-2,4-diamino-6-chloropyrimidine-5-carbaldehydes. The reaction takes place with hydrolysis of amino-group and chlorine. Particularly valuable features of this method included the broader substrate scope and operational simplicity as well as increased safety for small-scale high-speed synthesis.     

Synthesis, structural elucidation and catalytic activity toward a model Mizoroki-Heck C-C coupling reaction of the pyrazolic Tröger’s base Pd4Cl8(PzTB)2 complex

The synthesis of a novel palladium (II) complex Pd₄Cl₈(PzTB)₂, where PzTB is a pyrazole Tröger’s base analogue ligand is reported. A complete structure elucidation of the complex was achieved by spectroscopic and crystallographic data, exhibiting a metallomacrocycle supramolecular structure and a planar-square geometry on each palladium atom. This complex exhibited also a high activity and selectivity toward a model Mizoroki-Heck C-C coupling reaction of styrene with some iodobenzene derivatives.     

Avoiding gas-phase calculations in theoretical p<Emphasis Type="Italic">K</Emphasis><Subscript>a</Subscript> predictions

CBS-QB3, two simplified and less computationally demanding versions of CBS-QB3, DFT-B3LYP, and HF quantum chemistry methods have been used in conjunction with the CPCM continuum solvent model to calculate the free energies of proton exchange reactions in water solution following an isodesmic reaction approach. According to our results, the precision of the predicted pK _a values when compared to experiment is equivalent to that of the thermodynamic cycles that combine gas-phase and solution-phase calculations. However, in the aqueous isodesmic reaction schema, the accuracy of the results is less sensitive to the presence of explicit water molecules and to the global charges of the involved species since the free energies of solvation are not required. In addition, this procedure makes easier the prediction of pK _a values for molecules that undergo large conformational changes in solvation process and makes possible the pK _a prediction of unstable species in gas-phase such as some zwitterionic tautomers. The successive pK _a values of few amino acids corresponding to the ionization of the α-carboxylic acid and α-amine groups, which is one of the problematic cases for thermodynamic cycles, were successfully calculated by employing the aqueous isodesmic reaction yielding mean absolute deviations of 0.22 and 0.19 pK _a units for the first and second ionization processes, respectively.