Characterization of a Namban folding screen from the Edo period by means of EDXRF,SEM‐EDS and Raman spectroscopy

In this work, a multianalytical approach is employed to characterize the materials used in a Namban folding screen that depicts the arrival of the Portuguese to the port of Nagasaki. Portuguese sailors reached Japan in 1543 and initiated what was to be known as the Namban trade. This interaction between Portuguese and Japanese was meticulously recorded by artists in the form of valuable and rare folding screens. The present screen, attributed to the Edo period (~1603–1868), is what we could consider a second‐generation screen, a copy of scenes and characters that appear in screens from the Momoyama period (~1573–1603) but in increased scale and minor detail. The materials used in the screen were identified by means of in situ energy dispersive X‐ray fluorescence. Complementary results were obtained by Raman and scanning electron microscopy coupled to energy dispersive spectrometry analysis of microsamples taken from the screen. The palette used in this artwork resorts to gold, malachite, azurite, vermillion, red lead, white oyster shell, and carbon black. Differences were found, when compared with previously studied screens, i.e. the use of mixtures of pigments, namely vermillion with red lead in an orange shade of red and also the mixture of vermillion and carbon black to obtain a brown color. Special emphasis was given to the characterization of the golden areas and study of techniques of gold application. Copyright © 2013 John Wiley & Sons, Ltd.     

On behavior of the thixotropic fluids

In this work some aspects of constitutive equations for thixotropic fluids and restrictions on their functional forms are formally discussed. In the current study a special emphasis has been given to the structural nature of these substances. The behavior of thixotropic fluids is analyzed in terms of an isothermal laminar shear field with Brownian motion.     

Investigation of Cationic Polymerization of β‐Pinene Using Calorimetric Measurements

An experimental investigation of the kinetics of cationic polymerization of β‐pinene was performed using two different initiator systems under two different operating conditions (shot additions of initiator, and continuous feeding of monomer). The experiments were done using calorimetric measurements under isoperibolic conditions. The heat of polymerization of β‐pinene was found to be ?30.6 kcal · mol^?1. A simple kinetic model was tentatively proposed, and the model fit reasonably well to the different experimental runs. Different values of the fitting parameters were obtained for runs carried out under different conditions, which can probably be ascribed to the presence of adventitious impurities in the commercial‐grade monomer used.

     

Chemical and mineralogical characterization on glazes of ceramics from Coimbra (Portugal) from the sixteenth to nineteenth centuries

Chemical, mineralogical and textural characterizations were performed on glazed pieces prepared in laboratory as well as on faiences fragments collected from the existing remains in “Santa Clara-a-Velha” monastery (Coimbra, Portugal). The chemical investigation was carried out using micro X-ray fluorescence (μ-EDXRF) and wavelength dispersive X-ray fluorescence (WDXRF); the mineralogical results using X-ray diffraction (XRD) and the textural profile was obtained by scanning electron microscopy coupled with an energy dispersive spectroscopy system (SEM-EDS). Attention has been drawn to the glaze mineralogical changes during the firing temperature process, where three different types of glazes were submitted to three different firing temperatures (800 °C, 900 °C and 1,000 °C). Under these conditions, it is possible to relate the mineralogical content of the fragments to their firing temperature. Furthermore, we focused our purposes on identifying the technological aspects of the ceramic production in Coimbra, such as the raw materials, manufacture techniques and firing temperature adopted for the glaze. The latter aspect is highly dependent on the ceramic materials. In the framework of a more general project, this survey has as premise the recognition of a pattern, which is thought to be exclusively typical from the region of Coimbra. The perspective developed in the present work is towards reliable archaeometric criteria, which can be used to characterise scientifically the ceramics from Coimbra.     

Comprehensive analysis of maté (Ilex paraguariensis) compounds: development of chemical strategies for matesaponin analysis by mass spectrometry

Ilex paraguariensis (maté) is an important plant from southern Brazil, Paraguay, Uruguay and Argentina, where its leaves are widely used in hot or cold beverages. We now present a comprehensive ULPC-PDA-MS analysis of the compounds found in its leaves. The analysis was rapid, less than 13 min and many compounds were identified, among these, the chlorogenic acid series, and other quinic acid derivatives, xanthines, and several saponins, many of which have not been previously described, including many isomers. The isomerism could occur in the aglycone moiety, namely ursolic or oleanolic acid, or in the carbohydrate moiety. Additionally, many acetylated saponins were detected. The structure of known and novel saponins was determined using per-O-methylation with ESI-MS analysis, as well as with GC-MS of their partially O-methylated alditol acetate (PMAA) derivatives, along with ESI-MS analysis of the O-isopropylidene (IPP) derivatives provided fundamental information on interglycosidic linkages, avoiding the purification steps.     

Evaluation of Mechanical Properties and Water Vapor Permeability in Chitosan Biofilms Using Sorbitol and Glycerol

Summary: Chitosan biofilms were prepared with and without plasticizer (glycerol and sorbitol). The physical and mechanical properties of chitosan biofilms with and without plasticizer were evaluated. Chitosan was obtained from shrimp wastes and characterized. The film forming solution (FFS) was obtained through chitosan dissolution and drying. The solution had its pH adjusted to 6.0 and oven dried (40 °C, 24 h) with forced air circulation. Chitosan biofilms without plasticizer showed a tensile strength about 36% higher than biofilms produced with plasticizer. On the other hand, biofilms with plasticizer presented superior values of elongation. The permeability of the water vapor and color presented significant difference (p < 0.05) between all biofilms. Chitosan/plasticizer biofilms showed higher values of water vapor permeability in relation to chitosan biofilms without plasticizer.     

Thermodynamic and dynamic anomalies for a three-dimensional isotropic core-softened potential

Using molecular-dynamics simulations and integral equations (Rogers-Young, Percus-Yevick, and hypernetted chain closures) we investigate the thermodynamics of particles interacting with continuous core-softened intermolecular potential. Dynamic properties are also analyzed by the simulations. We show that, for a chosen shape of the potential, the density, at constant pressure, has a maximum for a certain temperature. The line of temperatures of maximum density (TMD) was determined in the pressure-temperature phase diagram. Similarly the diffusion constant at a constant temperature, D, has a maximum at a density rho(max) and a minimum at a density rho(min) < rho(max). In the pressure-temperature phase diagram the line of extrema in diffusivity is outside of the TMD line. Although this interparticle potential lacks directionality, this is the same behavior observed in simple point charge/extended water.     

Equation of state of charged colloidal suspensions and its dependence on the thermodynamic route

The thermodynamic properties of highly charged colloidal suspensions in contact with a salt reservoir are investigated in the framework of the renormalized Jellium model (RJM). It is found that the equation of state is very sensitive to the particular thermodynamic route used to obtain it. Specifically, the osmotic pressure calculated within the RJM using the contact value theorem can be very different from the pressure calculated using the Kirkwood-Buff fluctuation relations. On the other hand, Monte Carlo simulations show that both the effective pair potentials and the correlation functions are accurately predicted by the RJM. It is suggested that the lack of self-consistency in the thermodynamics of the RJM is a result of neglected electrostatic correlations between the counterions and coions.     

Multivariate curve resolution combined with gas chromatography to enhance analytical separation in complex samples: A review

This review describes the major advantages and pitfalls of iterative and non-iterative multivariate curve resolution (MCR) methods combined with gas chromatography (GC) data using literature published since 2000 and highlighting the most important combinations of GC coupled to mass spectrometry (GC–MS) and comprehensive two-dimensional gas chromatography with flame ionization detection (GC × GC-FID) and coupled to mass spectrometry (GC × GC–MS). In addition, a brief summary of some pre-processing strategies will be discussed to correct common issues in GC, such as retention time shifts and baseline/background contributions. Additionally, algorithms such as evolving factor analysis (EFA), heuristic evolving latent projection (HELP), subwindow factor analysis (SFA), multivariate curve resolution-alternating least squares (MCR-ALS), positive matrix factorization (PMF), iterative target transformation factor analysis (ITTFA) and orthogonal projection resolution (OPR) will be described in this paper. Even more, examples of applications to food chemistry, lipidomics and medicinal chemistry, as well as in essential oil research, will be shown. Lastly, a brief illustration of the MCR method hierarchy will also be presented.