Synthesis and Biological Studies of Pyrazolyl‐Diamine PtII Complexes Containing Polyaromatic DNA‐Binding Groups

New [PtCl(pz*NN)]ⁿ⁺ complexes anchored by pyrazolyl‐diamine (pz*NN) ligands incorporating anthracenyl or acridine orange DNA‐binding groups have been synthesized so as to obtain compounds that would display synergistic effects between platination and intercalation of DNA. Study of their interaction with supercoiled DNA indicated that the anthracenyl‐containing complex L²Pt displays a covalent type of binding, whereas the acridine orange counterpart L³Pt shows a combination of intercalative and covalent binding modes with a strong contribution from the former. L²Pt showed a very strong cytotoxic effect on ovarian carcinoma cell lines A2780 and A2780cisR, which are, respectively, sensitive to and resistant to cisplatin. In these cell lines, L²Pt is nine to 27 times more cytotoxic than cisplatin. In the sensitive cell line, L³Pt showed a cytotoxic activity similar to that of cisplatin, but like L²Pt was able significantly to overcome cisplatin cross‐resistance. Cell‐uptake studies showed that L²Pt accumulates preferentially in the cytoplasm, whereas L³Pt reaches the cell nucleus more easily, as clearly visualized by time‐lapse confocal imaging of live A2870 cells. Altogether, these findings seem to indicate that interaction with biological targets other than DNA might be involved in the mechanism of action of L²Pt because this compound, despite having a weaker ability to target the cell nucleus than L³Pt , as well as an inferior DNA affinity, is nevertheless more cytotoxic. Furthermore, ultrastructural studies of A2870 cells exposed to L²Pt and L³Pt revealed that these complexes induce different alterations in cell morphology, thus indicating the involvement of different modes of action in cell death.     

Antitumor Activity of Ionic Liquids Based on Ampicillin

Significant antiproliferative effects against various tumor cell lines were observed with novel ampicillin salts as ionic liquids. The combination of anionic ampicillin with appropriate ammonium, imidazolium, phosphonium, and pyridinium cations yielded active pharmaceutical ingredient ionic liquids (API‐ILs) that show potent antiproliferative activities against five different human cancer cell lines: T47D (breast), PC3 (prostate), HepG2 (liver), MG63 (osteosarcoma), and RKO (colon). Some API‐ILs showed IC₅₀ values between 5 and 42 nM , activities that stand in dramatic contrast to the negligible cytotoxic activity level shown by the ampicillin sodium salt. Moreover, very low cytotoxicity against two primary cell lines—skin (SF) and gingival fibroblasts (GF)—indicates that the majority of these API‐ILs are nontoxic to normal human cell lines. The most promising combination of antitumor activity and low toxicity toward healthy cells was observed for the 1‐hydroxyethyl‐3‐methylimidazolium–ampicillin pair ([C₂OHMIM][Amp]), making this the most suitable lead API‐IL for future studies.     

Strongly Photosensitive and Fluorescent F8T2 Electrospun Fibers

Electrospun fibers of poly[(9,9‐dioctylfluorenyl‐2,7‐diyl)‐co‐bithiophene] (F8T2) with exceptional electro‐optical performance are obtained. The I/T characteristics measured in fibers with 7–15 µm diameter and 1 mm length show a semiconductor behavior; their thermal activation energy is 0.5 eV and the dark conductivity at RT is 5 × 10^?9 (Ω cm)^?1. Besides exhibiting a photosensitivity of about 60 under white light illumination with a light power intensity of 25 mW · cm^?2, the fibers also attain RT photoluminescence in the cyan, yellow, and red wavelength range under ultraviolet, blue, and green light excitation, respectively. Optical microscope images of F8T2 reveal homogeneous electrospun fibers, which are in good agreement with the uniformly radial fluorescence observed.

     

Crystallization kinetics of thermoplastic elastomeric blends based on ground tyre rubber

This work analyzes the crystallization process of thermoplastic elastomeric blends (TPE) based on ground tyre rubber (GTR). More specifically it analyzes the effect of GTR and fresh rubber materials, like ethylene propylene diene monomer (EPDM) and ethylene propylene rubber (EPR), on the crystallization of binary and ternary polypropylene (PP)‐based blends. The crystallization kinetics is studied under isothermal and nonisothermal conditions using differential scanning calorimetry (DSC). The kinetic parameters derived from the Avrami model are used to study the effect of temperature and rubber materials on the nucleation mechanism, the morphology of the crystalline structures, and the crystallization rate. Results reveal that GTR has a strong nucleating effect on PP and that its presence leads to higher crystallization rates. The EPDM presence has a slight effect on the PP crystallization process whereas EPR has no significant effect. From the DSC curves it is possible to detect an inverse relationship between temperature and the crystallization rate. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42589.     

Evaluation of incremental learning algorithms for HMM in the recognition of alphanumeric characters

We present an evaluation of incremental learning algorithms for the estimation of hidden Markov model (HMM) parameters. The main goal is to investigate incremental learning algorithms that can provide as good performances as traditional batch learning techniques, but incorporating the advantages of incremental learning for designing complex pattern recognition systems. Experiments on handwritten characters have shown that a proposed variant of the ensemble training algorithm, employing ensembles of HMMs, can lead to very promising performances. Furthermore, the use of a validation dataset demonstrated that it is possible to reach better performances than the ones presented by batch learning.     

Volatile fraction of DOP “Castelo Branco” cheese: Influence of breed

“Castelo Branco” cheese is a Portuguese DOP cheese made from raw ewe’s milk coagulated with Cynara cardunculus, ripened for at least 40 days. “Merino da Beira Baixa” pure race is frequently used to produce milk for this cheese, however, exotic races such as Assaf and crusade of these two races are also used. The aim of this work has been to compare the volatile profile and sensory characteristics of DOP “Castelo Branco” cheeses manufactured during winter season with milk of breeds from Merino, Assaf and crusade of these two races and identify volatile compounds that can distinguish these cheeses.     

Catalytic performance of silica-aluminas synthesised with the help of chitosan biopolymer

Mesoporous amorphous silica-aluminas were synthesised with standard aluminium and silicon sources by means of the formation of inorganic–organic composites with the addition of chitosan biopolymer, and compared to analogous catalysts synthesised conventionally. Some catalysts were subjected to hydrothermal treatment. The resulting specific surface areas were from 480 to 573 m²/g in the untreated samples and 300–430 m²/g in the hydrotreated catalysts, average pore sizes ranging from 32 to 100 Å with sharp, unimodal distributions. The chitosan materials showed higher specific surface areas and larger pore sizes than those of their non-chitosan counterparts. The most important differences in the acidic properties were in the relationships between tetrahedral and octahedral aluminium atoms, the chitosan materials having higher relative amounts of tetrahedral aluminium than the conventional silica-aluminas. Evidences of stabilization in the physical and chemical properties were observed in the chitosan-containing catalysts. The catalytic performance was evaluated with the conversion of tri-isopropylbenzene at 400 °C, to assess activity and accessibility, and cyclohexene at 300 °C, to assess hydrogen transfer properties. The highest activity and accessibility was observed in the hydrotreated, chitosan-containing catalyst, while hydrogen transfer capabilities were similar to those of medium unit cell sizes, equilibrium commercial FCC catalysts.     

Numerical Modelling of Thin-Walled Stainless Steel Structural Elements in Case of Fire

In this paper, the structural response of stainless steel thin-walled elements submitted to fire is analysed numerically by means of the geometrically and materially non-linear Finite Element program SAFIR, including imperfections. In order to make these simulations, two main changes in the program were made: (i) the code was changed in order to deal with the stainless steel 2D material constitutive law to be used with shell elements and (ii) the possibility of the program to take into account residual stresses with shell finite elements was introduced. The stainless steel stress–strain relationship at high temperatures was based on the one presented in part 1.2 of Eurocode 3. To model the strain hardening exhibited by the stainless steels, using the shell element formulation, an approximation to the Eurocode 3 constitutive law was needed. Local and global geometrical imperfections were considered in the simulations. The paper shows the influence of the residual stresses on the ultimate load-carrying capacity of thin-walled stainless steel structural elements in case of fire.     

Artificial neural networks for machining processes surface roughness modeling

In recent years, several papers on machining processes have focused on the use of artificial neural networks for modeling surface roughness. Even in such a specific niche of engineering literature, the papers differ considerably in terms of how they define network architectures and validate results, as well as in their training algorithms, error measures, and the like. Furthermore, a perusal of the individual papers leaves a researcher without a clear, sweeping view of what the field’s cutting edge is. Hence, this work reviews a number of these papers, providing a summary and analysis of the findings. Based on recommendations made by scholars of neurocomputing and statistics, the review includes a set of comparison criteria as well as assesses how the research findings were validated. This work also identifies trends in the literature and highlights their main differences. Ultimately, this work points to underexplored issues for future research and shows ways to improve how the results are validated.     

Views and Patterns in E-Commerce Application Design

Separation of concerns is a well-established principle in software engineering that supports reuse by hiding complexity through abstraction mechanisms. The Abstract Design Views model was created with reuse in mind and allows the designer to apply separation of concerns in a software system from the design to the implementation. In this model, viewed objects represent the basic concern, i.e., the algorithms that provide the essential functionality relevant to an application domain, and viewer objects represent the special concerns related to other software issues, such as user interface presentation, synchronization, and timing. In this paper we use a reuse taxonomy to analyze and validate this model. Using this analysis and the properties of the relationship between viewer and viewed objects, called views, we also indicate how to map the views-based designs into implementations based on design patterns that satisfy the views properties. Finally, we show how to apply the principles of our approach, using views and the design patterns, to design e-commerce applications.