Synthesis,Characterization and Evaluation of the Antibacterial and Antitumor Activity of HalogenatedSalen Copper (II) Complexes derived from Camphoric Acid

Platinum metal complexes are the most common chemotherapeutics currently used in cancer treatment. However, the frequent adverse effects, as well as acquired resistance by tumor cells, urge the development of effective alternatives. In the recent past, copper complexes with Schiff base ligands have emerged as good alternatives, showing interesting results. Accordingly, and in continuation of previous studies in this area, three new camphoric acid-derived halogenated salen ligands and their corresponding Cu (II) complexes were synthesized and their antitumor activity was evaluated in order to determine the influence of the type and number of halogens present (Br, Cl). The in vitro cytotoxic activity was screened against colorectal WiDr and LS1034 and against breast MCF-7 and HCC1806 cancer cell lines. The results proved the halogenated complexes to be very efficient, the tetrachlorinated Cu (II) complex being the most promising, presenting IC₅₀ of 0.63–1.09 μM for the cell lines studied. The complex also shows selectivity to colorectal cancer cells compared to non-tumor colon cells. It is worth highlighting that the tetrachlorinated Cu (II) complex, our most efficient complex, shows a significantly more powerful antitumor effect than the reference drugs currently used in conventional chemotherapy. The halogenated salen and corresponding complexes were also screened for their antimicrobial activity against four bacterial species-Staphylococcus aureus, Enterococcus faecalis, Escherichia coli and Pseudomonas aeruginosa-and four fungal species-Candida albicans, Candida glabrata, Aspergillus fumigatus and Alternaria alternata. The compounds were found to exhibit moderate to strong antibacterial activity against the bacterial strains studied. NMR studies and theoretical calculations provided some insight into the structure of the ligands and copper complexes. Considering the results presented herein, our work validates the potential use of copper-based chemotherapeutics as alternatives for cancer treatment.     

Molecular Hybridization Strategy on the Design,Synthesis, and Structural Characterization of Ferrocene-N-acyl Hydrazones as Immunomodulatory Agents

Immunomodulatory agents are widely used for the treatment of immune-mediated diseases, but the range of side effects of the available drugs makes necessary the search for new immunomodulatory drugs. Here, we investigated the immunomodulatory activity of new ferrocenyl-N-acyl hydrazones derivatives (SintMed(141–156). The evaluated N-acyl hydrazones did not show cytotoxicity at the tested concentrations, presenting CC₅₀ values greater than 50 µM. In addition, all ferrocenyl-N-acyl hydrazones modulated nitrite production in immortalized macrophages, showing inhibition values between 14.4% and 74.2%. By presenting a better activity profile, the ferrocenyl-N-acyl hydrazones SintMed149 and SintMed150 also had their cytotoxicity and anti-inflammatory effect evaluated in cultures of peritoneal macrophages. The molecules were not cytotoxic at any of the concentrations tested in peritoneal macrophages and were able to significantly reduce (p < 0.05) the production of nitrite, TNF-α, and IL-1β. Interestingly, both molecules significantly reduced the production of IL-2 and IFN-γ in cultured splenocytes activated with concanavalin A. Moreover, SintMed150 did not show signs of acute toxicity in animals treated with 50 or 100 mg/kg. Finally, we observed that ferrocenyl-N-acyl hydrazone SintMed150 at 100 mg/kg reduced the migration of neutrophils (44.6%) in an acute peritonitis model and increased animal survival by 20% in an LPS-induced endotoxic shock model. These findings suggest that such compounds have therapeutic potential to be used to treat diseases of inflammatory origin.     

Gamma radiation effects on physical properties of parchment documents: Assessment of Dmax

Parchments are important documents that give testimony for History; therefore these materials should be respected and preserved. Considering incremental biodeterioration problems that have to be faced daily, the Archive of the University of Coimbra (AUC) is involved in different scientific projects in order to evaluate and determine new methods for document decontamination and preservation.The aim of this study was to evaluate gamma radiation effects on the colour and texture of the AUC parchment documents. The assessment of these effects was used to estimate the maximum gamma radiation dose (D_max) that could guarantee parchment documents′ decontamination treatment, without significant alteration of their physical properties. Parchment samples were exposed to gamma radiation doses ranging from 10 to 30 kGy. The texture and colour of samples were assessed before and after the irradiation procedure, using a texture analyser and an electronic colorimeter. Hardness and springiness were determined based on texture spectra. Lightness (L?), Chroma (C), greenness vs. redness (a*) and yellowness vs. blueness (b*) values were obtained from colorimetric measures. Results indicate no significant effects of gamma radiation on the texture and colour of parchment for the studied doses.     

Electrospray ionization mass spectrometry and partial least squares discriminant analysis applied to the quality control of olive oil

Direct infusion electrospray ionization mass spectrometry in the positive ion mode [ESI(+)‐MS] is used to obtain fingerprints of aqueous–methanolic extracts of two types of olive oils, extra virgin (EV) and ordinary (OR), as well as of samples of EV olive oil adulterated by the addition of OR olive oil and other edible oils: corn (CO), sunflower (SF), soybean (SO) and canola (CA). The MS data is treated by the partial least squares discriminant analysis (PLS‐DA) protocol aiming at discriminating the above‐mentioned classes formed by the genuine olive oils, EV (1) and OR (2), as well as the EV adulterated samples, i.e. EV/SO (3), EV/CO (4), EV/SF (5), EV/CA (6) and EV/OR (7). The PLS‐DA model employed is built with 190 and 70 samples for the training and test sets, respectively. For all classes (1–7), EV and OR olive oils as well as the adulterated samples (in a proportion varying from 0.5 to 20.0% w/w) are properly classified. The developed methodology required no ions identification and demonstrated to be fast, as each measurement lasted about 3 min including the extraction step and MS analysis, and reliable, because high sensitivities (rate of true positives) and specificities (rate of true negatives) were achieved. Finally, it can be envisaged that this approach has potential to be applied in quality control of EV olive oils. Copyright © 2013 John Wiley & Sons, Ltd.     

Cotype and absolutely summing linear operators

New applications of cotype to the theory of absolutely summing linear operators between Banach spaces are proved in this paper. Among other consequences we extend/complement some classical results of Bennett (Duke Math J 44:603?C639, 1977) on the existence of non-absolutely summing operators between ? _p spaces and of Davis and Johnson (Stud Math 51:81?C85, 1974) on the existence of compact non-absolutely summing linear operators. We also point out that some of our results are sharp.     

A Note on Feynman Path Integral for Electromagnetic External Fields

We propose a Fresnel stochastic white noise framework to analyze the nature of the Feynman paths entering on the Feynman Path Integral expression for the Feynman Propagator of a particle quantum mechanically moving under an external electromagnetic time-independent potential.     

Li‐doped nanosized TiO2 powder with enhanced photocalatylic acivity under sunlight irradiation

This work reports on the synthesis of Li‐doped TiO₂ nanoparticles using the sol–gel process and solid‐state sintering, and investigates their potential use as a photocatalyst for degradation under sunlight excitation of different organic model compounds in aqueous solution. The structure of the nanocrystals was examined by X‐ray diffraction, UV‐vis ground state diffuse reflectance absorption spectra and X‐ray photoelectron emission spectroscopy. Results showed that samples prepared by sol–gel process and calcined at 400 °C are composed of a mixture of anatase and rutile phases, in contrast to the one prepared by solid‐state sintering, which exhibits an anatase phase with Li being involved in a spinel phase. The photocatalytic degradation of aqueous solutions of different aromatic compounds was successfully achieved under sunlight excitation in presence of Li‐doped TiO₂ prepared via sol–gel process. It was shown that the calcination temperature and the preparation mode greatly affect the photocatalytic efficiency. Copyright © 2010 John Wiley & Sons, Ltd.     

Summability and estimates for polynomials and multilinear mappings

In this paper we extend and generalize several known estimates for homogeneous polynomials and multilinear mappings on Banach spaces. Applying the theory of absolutely summing nonlinear mappings, we prove that estimates which are known for mappings on ?_p spaces in fact hold true for mappings on arbitrary Banach spaces.     

A polynomial Hutton theorem with applications

Extending a classical linear result due to Hutton to a nonlinear setting, we prove that a continuous homogeneous polynomial between Banach spaces can be approximated by finite rank polynomials if and only if its adjoint can be approximated by finite rank linear operators. Among other consequences, we apply this result to generalize a classical result due to Aron and Schottenloher about the approximation property on spaces of polynomials and a recent result due to Çaliskan and Rueda about the quasi-approximation property on projective symmetric tensor products.     

Luminescence quantum yield determination for molecules adsorbed onto solid powdered particles.

A new methodology for the determination of the fluorescence quantum yield of dyes adsorbed onto microcrystalline cellulose is presented and applied to rhodamine 101, cresyl violet and auramine O. It is based on a previously reported method by Ruetten and Thomas (J. Phys. Chem., 1998, 102, 598-606), which is not applicable to the dyes used in the present study. It uses ground-state diffuse reflectance spectra obtained with and without filters, which prevents the luminescence of the dye from reaching the integrating sphere and the photodetector. New equations are presented here, correcting for the fluorescence emission of the dye, which depends on the detector sensitivity. Cut-on filters, which have a transmittance close to unity in the absorption region, and close to zero in the emission region, of the dye are used to obtain corrected reflectance spectra. The influence of the substrate was also taken into account. This methodology may be applied to other probes and surfaces or emissions of a different nature (i.e., phosphorescence or delayed fluorescence), and constitutes a very simple and general procedure to solve the important problem of luminescence quantum yield determination of probes adsorbed onto solid powdered surfaces.