The Mechanical and Biological Performance of Photopolymerized Gelatin-Based Hydrogels as a Function of the Reaction Media

From the first experiments with biomaterials to mimic tissue properties, the mechanical and biochemical characterization has evolved extensively. Several properties can be described, however, what should be essential is to conduct a proper and physiologically relevant characterization. Herein, the influence of the reaction media (RM) and swelling media (SM)–phosphate buffered saline (PBS) and Dulbecco's modified Eagle's medium (DMEM) with two different glucose concentrations–is described in gelatin methacrylamide (GelMA) hydrogel mechanics and in the biological behavior of two tumoral cell lines (Caco-2 and HCT-116). All scaffolds are UV-photocrosslinked under identical conditions and evaluated for mass swelling ratio and stiffness. The results indicate that stiffness is highly susceptible to the RM, but not to the SM. Additionally, PBS-prepared hydrogels exhibited a higher photopolymerization degree according to high resolution magic-angle spinning (HR-MAS) NMR. These findings correlate with the biological response of Caco-2 and HCT-116 cells seeded on the substrates, which demonstrated flatter morphologies on stiffer hydrogels. Overall, cell viability and proliferation are excellent for both cell lines, and Caco-2 cells displayed a characteristic apical-basal polarization based on F-actin/Nuclei fluorescence images. These characterization experiments highlight the importance of conducting mechanical testing of biomaterials in the same medium as cell culture.     

The Role of Mechanical Properties and Structure of Type I Collagen Hydrogels on Colorectal Cancer Cell Migration

Mechanical interactions between cells and their microenvironment play an important role in determining cell fate, which is particularly relevant in metastasis, a process where cells invade tissue matrices with different mechanical properties. In vitro, type I collagen hydrogels have been commonly used for modeling the microenvironment due to its ubiquity in the human body. In this work, the combined influence of the stiffness of these hydrogels and their ultrastructure on the migration patterns of HCT-116 and HT-29 spheroids are analyzed. For this, six different types of pure type I collagen hydrogels by changing the collagen concentration and the gelation temperature are prepared. The stiffness of each sample is measured and its ultrastructure is characterized. Cell migration studies are then performed by seeding the spheroids in three different spatial conditions. It is shown that changes in the aforementioned parameters lead to differences in the mechanical stiffness of the matrices as well as the ultrastructure. These differences, in turn, lead to distinct cell migration patterns of HCT-116 and HT-29 spheroids in either of the spatial conditions tested. Based on these results, it is concluded that the stiffness and the ultrastructural organization of the matrix can actively modulate cell migration behavior in colorectal cancer spheroids.     

Micro‐EDXRF study of Chalcolithic copper‐based artefacts from Southern Portugal

A collection of 39 metallic artefacts recovered in archaeological sites of Southern Portugal was studied by micro‐EDXRF to identify their compositions and the use of metal among ancient communities. Artefacts presented different typologies such as tools (e.g. awls, chisels and a saw) and weapons (e.g. daggers and arrowheads) mostly belonging to 2500–2000 BC. The results show copper with variable amounts of As and very low content of other impurities, such as Fe, Pb or Sb. Moreover, nearly half of the collection is composed by arsenical copper alloys, and an association was found between arsenic content and typology because the weapons group (mostly daggers) present higher values than tools (mostly awls). These results suggest some criteria in the selection of arsenic‐rich copper ores or smelting products. Finally, the compositions were compared to those of other collections from neighbouring regions and different chronology to determine metallurgical parallels. Copyright © 2015 John Wiley & Sons, Ltd.     

Application of p-Adic Wavelets to Model Reaction–Diffusion Dynamics in Random Porous Media

Fourier and more generally wavelet analysis over the fields of p-adic numbers are widely used in physics, biology and cognitive science, and recently in geophysics. In this note we present a model of the reaction–diffusion dynamics in random porous media, e.g., flow of fluid (oil, water or emulsion) in a a complex network of pores with known topology. Anomalous diffusion in the model is represented by the system of two equations of reaction–diffusion type, for the part of fluid not bound to solid’s interface (e.g., free oil) and for the part bound to solid’s interface (e.g., solids–bound oil). Our model is based on the p-adic (treelike) representation of pore-networks. We present the system of two p-adic reaction–diffusion equations describing propagation of fluid in networks of pores in random media and find its stationary solutions by using theory of p-adic wavelets. The use of p-adic wavelets (generalizing classical wavelet theory) gives a possibility to find the stationary solution in the analytic form which is typically impossible for anomalous diffusion in the standard representation based on the real numbers.     

Generalized three-sided assignment markets: core consistency and competitive prices

A generalization of the classical three-sided assignment market is considered, where value is generated by pairs or triplets of agents belonging to different sectors, as well as by individuals. For these markets we represent the situation that arises when some agents leave the market with some payoff by means of a generalization of Owen (Ann Econ Stat 25–26:71–79, 1992) derived market. Consistency with respect to the derived market, together with singleness best and individual anti-monotonicity, axiomatically characterize the core for these generalized three-sided assignment markets. When one sector is formed by buyers and the other by two different type of sellers, we show that the core coincides with the set of competitive equilibrium payoff vectors.     

XDS: a flexible beamline for X‐ray diffraction and spectroscopy at the Brazilian synchrotron

The majority of the beamlines at the Brazilian Synchrotron Light Source Laboratory (LNLS) use radiation produced in the storage‐ring bending magnets and are therefore currently limited in the flux that can be used in the harder part of the X‐ray spectrum (above ～10 keV). A 4 T superconducting multipolar wiggler (SCW) was recently installed at LNLS in order to improve the photon flux above 10 keV and fulfill the demands set by the materials science community. A new multi‐purpose beamline was then installed at the LNLS using the SCW as a photon source. The XDS is a flexible beamline operating in the energy range between 5 and 30 keV, designed to perform experiments using absorption, diffraction and scattering techniques. Most of the work performed at the XDS beamline concentrates on X‐ray absorption spectroscopy at energies above 18 keV and high‐resolution diffraction experiments. More recently, new setups and photon‐hungry experiments such as total X‐ray scattering, X‐ray diffraction under high pressures, resonant X‐ray emission spectroscopy, among others, have started to become routine at XDS. Here, the XDS beamline characteristics, performance and a few new experimental possibilities are described.     

Synthesis of novel tetrahydroindeno[1,2-b]pyrrolidines via Ugi multicomponent and palladium-catalyzed aerobic oxidative cyclization

Novel tetrahydroindeno[1,2-b]pyrrolidines were conveniently prepared in moderate to good yields via a sequential Ugi multicomponent reaction or Staudinger/aza-Wittig/Ugi combination, followed by the palladium-catalyzed aerobic oxidative cyclization of the resulting Ugi adducts.     

Microemulsion electrokinetic chromatography as a suitable tool for lipophilicity determination of acidic,neutral, and basic compounds

In the present work, several MEEKC systems are studied to assess their suitability for lipophilicity determination of acidic, neutral, and basic compounds. Thus, several microemulsion compositions over a wide range of pH values (from 2.0 to 12.0), containing heptane, 1?butanol and different types and amounts of surfactant (SDS or sodium cholate: from 1.3 to 3.3%) are characterized using Abraham's solvation model. The addition of acetonitrile (up to 10%) is also studied, since it increases the resolution of the technique for the most lipophilic compounds. The system coefficients obtained are very similar to those of the 1?octanol/water, used as the reference lipophilicity index, allowing simple and linear correlations between the 1?octanol/water partition values (log P_o/w) and MEEKC mass distribution ratios (log k_MEEKC). Variations in the microemulsion composition (aqueous buffer, surfactant, concentration of ACN) did not significantly affect the similarity of the MEEKC systems to log P_o/w partition.