Molecular photoionization cross sections in electron propagator theory: angular distributions beyond the dipole approximation

Corrections to dipole approximation results for angular distributions in photoionization of first-row hydrides have determined by using Dyson orbitals calculated with ab initio electron propagator theory and by considering the full multipole expansion for the incident photon representation. The relative importance of first-order corrections which consist of electric quadrupole and magnetic dipole terms and of higher-order terms has been estimated as a function of photon energy. Multipole corrections to the dipole approximation depend on photon energy and on the characteristics of the Dyson orbitals.     

Ultrasensitive small molecule fluorogenic probe for human heparanase

Heparanase (HPA) is a critical enzyme involved in the remodeling of the extracellular matrix (ECM), and its elevated expression has been linked with diseases such as various types of cancer and inflammation. The detection of heparanase enzymatic activity holds tremendous value in the study of the cellular microenvironment, and search of molecular therapeutics targeting heparanase, however, no structurally defined probes are available for the detection of heparanase activity. Here we present the development of the first ultrasensitive fluorogenic small-molecule probe for heparanase enzymatic activity via tuning the electronic effect of the substrate. The probe exhibits a 756-fold fluorescence turn-on response in the presence of human heparanase, allowing one-step detection of heparanase activity in real-time with a picomolar detection limit. The high sensitivity and robustness of the probe are exemplified in a high-throughput screening assay for heparanase inhibitors.

Heparanase, a critical enzyme involved in the remodeling of the extracellular matrix, activates a disaccharide probe HADP to give a strong fluorescence signal.     

Impact dynamics of multibody systems with frictional contact using joint coordinates and canonical equations of motion

This paper presents a methodology in computational dynamics for the analysis of mechanical systems that undergo intermittent motion. A canonical form of the equations of motion is derived with a minimal set of coordinates. These equations are used in a procedure for balancing the momenta of the system over the period of impact, calculating the jump in the body momentum, velocity discontinuities and rebounds. The effect of dry friction is discussed and a contact law is proposed. The present formulation is extended to open and closed-loop mechanical systems where the jumps in the constraints' momenta are also solved. The application of this methodology is illustrated with the study of impact of open-loop and closed-loop examples.     

Assessing the antioxidative properties and chemical composition of Linaria vulgaris infusion

The ability of Linaria vulgaris (Scrophulariaceae) infusion to act as a scavenger of 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical, reactive oxygen species (superoxide radical, hydroxyl radical, hypochlorous acid (HOCl)) and nitric oxide was investigated. The obtained data indicate that the infusion has a good scavenging activity against superoxide radical and is a very potent nitric oxide and DPPH scavenger. In hydroxyl radical assay a pro-oxidant capacity was noticed, especially for concentrations higher than 31.25 microg mL(-1). No effect was found against HOCl. A phytochemical study of this extract was also performed. The HPLC/UV analysis allowed the identification and quantification of eight organic acids (oxalic, aconitic, citric, ketoglutaric, ascorbic, malic, shikimic and fumaric acids). The phenolic composition of the lyophilised infusion was also determined by HPLC/DAD and four compounds were quantified, but, despite its high content, only linarin was managed to be identified.     

Valorization of Fly Ashes and Sands Wastes from Biomass Boilers in One-Part Geopolymers

Fly ash (FA) and exhausted bed sands (sands wastes) that are generated in biomass burners for energy production are two of the wastes generated in the pulp and paper industry. The worldwide production of FA biomass is estimated at 10 million tons/year and is expected to increase. In this context, the present work aims to develop one-part alkali-activated materials with biomass FA (0–100 wt.% of the binder) and sands wastes (100 wt.% of the aggregate). FA from two different boilers, CA and CT, was characterized and the mortar’s properties, in the fresh and hardened conditions, were evaluated. Overall, the incorporation of FA decreases the compressive strength of the specimens. However, values higher than 30 MPa are reached with 50 wt.% of FA incorporation. For CA and CT, the compressive strength of mortars with 28 days of curing was 59.2 MPa (0 wt.%), 56.9 and 57.0 MPa (25 wt.%), 34.9 and 46.8 MPa (50 wt.%), 20.5 and 13.5 MPa (75 wt.%), and 9.2 and 0.2 MPa (100 wt.%), respectively. The other evaluated characteristics (density, water absorption, leached components and freeze–thaw resistance) showed no significant differences, except for the specimen with 100 wt.% of CA. Therefore, this work proved that one-part geopolymeric materials with up to 90 wt.% of pulp and paper industrial residues (FA and sand) can be produced, thus reducing the carbon footprint associated with the construction sector.     

Numerical solution of the generalized Serre equations with the MacCormack finite-difference scheme

This paper describes a two-dimensional numerical model to solve the generalized Serre equations. In order to solve the system equations, written in the conservative form, we use an explicit finite-difference method based on the MacCormack time-splitting scheme. The numerical method and the computational model are validated by comparing one- and two-dimensional numerical solutions with theoretical and experimental results. Finally, the two-dimensional model (in a horizontal plane) is tested in a domain with complicated boundary conditions.     

Validation of the uncertainty evaluation for the determination of metals in solid samples by atomic spectrometry

 Every analytical result should be expressed with some indication of its quality. The uncertainty as defined by Eurachem ("parameter associated with the result of a measurement that characterises the dispersion of the values that could reasonably be attributed to the, . . ., quantity subjected to measurement") is a good tool to accomplish this goal in quantitative analysis. Eurachem has produced a guide to the estimation of the uncertainty attached to an analytical result. Indeed, the estimation of the total uncertainty by using uncertainty propagation laws is components-dependent. The estimation of some of those components is based on subjective criteria. The identification of the uncertainty sources and of their importance, for the same method, can vary from analyst to analyst. It is important to develop tools which will support each choice and approximation. In this work, the comparison of an estimated uncertainty with an experimentally assessed one, through a variance test, is performed. This approach is applied to the determination by atomic absorption of manganese in digested samples of lettuce leaves. The total uncertainty estimation is calculated assuming 100% digestion efficiency with negligible uncertainty. This assumption was tested. Received: 3 November 1997 · Accepted: 2 January 1998     

Surface waves propagation in shallow water: A finite element model

A two-dimensional (in-plane) numerical model for surface waves propagation based on the non-linear dispersive wave approach described by Boussinesq-type equations, which provide an attractive theory for predicting the depth-averaged velocity field resulting from that wave-type propagation in shallow water, is presented. The numerical solution of the corresponding partial differential equations by finite-difference methods has been the subject of several scientific works. In the present work we propose a new approach to the problem: the spatial discretization of the system composed by the Boussinesq equations is made by a finite element method, making use of the weighted residual technique for the solution approach within each element. The model is validated by comparing numerical results with theoretical solutions and with results obtained experimentally.     

A high‐order Petrov–Galerkin finite element method for the classical Boussinesq wave model

A high‐order Petrov–Galerkin finite element scheme is presented to solve the one‐dimensional depth‐integrated classical Boussinesq equations for weakly non‐linear and weakly dispersive waves. Finite elements are used both in the space and the time domains. The shape functions are bilinear in space–time, whereas the weighting functions are linear in space and quadratic in time, with C⁰‐continuity. Dispersion correction and a highly selective dissipation mechanism are introduced through additional streamline upwind terms in the weighting functions. An implicit, conditionally stable, one‐step predictor–corrector time integration scheme results. The accuracy and stability of the non‐linear discrete equations are investigated by means of a local Taylor series expansion. A linear spectral analysis is used for the full characterization of the predictor–corrector inner iterations. Based on the order of the analytical terms of the Boussinesq model and on the order of the numerical discretization, it is concluded that the scheme is fourth‐order accurate in terms of phase velocity. The dissipation term is third order only affecting the shortest wavelengths. A numerical convergence analysis showed a second‐order convergence rate in terms of both element size and time step. Four numerical experiments are addressed and their results are compared with analytical solutions or experimental data available in the literature: the propagation of a solitary wave, the oscillation of a flat bottom closed basin, the oscillation of a non‐flat bottom closed basin, and the propagation of a periodic wave over a submerged bar. Copyright © 2008 John Wiley & Sons, Ltd.     

Composition of quince (Cydonia oblonga Miller) seeds: phenolics, organic acids and free amino acids

Phenolic compounds, organic acids and free amino acids of quince seeds were determined by HPLC/DAD, HPLC/UV and GC/FID, respectively. Quince seeds presented a phenolic profile composed of 3-O-caffeoylquinic, 4-O-caffeoylquinic, 5-O-caffeoylquinic and 3,5-dicaffeoylquinic acids, lucenin-2, vicenin-2, stellarin-2, isoschaftoside, schaftoside, 6-C-pentosyl-8-C-glucosyl chrysoeriol and 6-C-glucosyl-8-C-pentosyl chrysoeriol. Six identified organic acids constituted the organic acid profile of quince seeds: citric, ascorbic, malic, quinic, shikimic and fumaric acids. The free amino acid profile was composed of 21 identified free amino acids and the three most abundant were glutamic and aspartic acids and asparagine.