Herein we report the synthesis, characterization, and photophysical and biological evaluation of the complexes Ln(DBM)3(RPhen) (Ln = Sm, R = H; Ln = Sm, Eu, Tb, R = 5-NH2) stabilized by three β-diketonate units (DBM) and a phenanthroline (RPhen) derivative, with the aim of contributing to the development of lanthanide-based compounds with potential application as anticancer agents. The UV-vis spectra of [Sm(DBM)3(Phen)], [Sm(DBM)3(NH2Phen)], [Eu(DBM)3(NH2Phen)] and [Tb(DBM)3(NH2Phen)] measured in DMSO and PBS showed a strong absorption band centered at ca. 350 nm in both solvents. In DMSO, all lanthanide compounds except [Sm(DBM)3(Phen)] show a ligand centered emission band at ca. 520 nm. In PBS only sharp emission peaks are detected. The complexes show similar cytotoxic effects in A2780 ovarian cancer cells, presenting IC50 values at 24 h in the range 16-27 μM. The measurement of the cellular uptake of the complexes in the A2780 cells by inductively coupled plasma mass spectrometry (ICP-MS) revealed preferential accumulation at the membrane and cytoskeleton, with the exception of [Sm(DBM)3(Phen)] that presented higher accumulation in the cytosol than in the cell membranes. All the evaluated lanthanide complexes showed low nuclear uptake, although not negligible. Spectroscopic studies on the interaction of the complexes with calf thymus DNA (ctDNA) revealed a moderate affinity with apparent binding constants in the 104 M-1 range. Complexes bind DNA not by intercalation but probably by electrostatic interactions. A morphological evaluation of the cells treated with the different complexes by electron microscopy (TEM/SEM) proved that all of them induce mitochondrial alterations, which seemed more pronounced for the NH2Phen complexes. In addition, the complex [Eu(DBM)3(NH2Phen)] presented lysosomal uptake that might explain its augmented cytotoxicity.

Analysis of Chemical Elements in Hair: historical perspective, capabilities, controversies and analytical challenges -elements in human hair, despite the uncertainties related with the validity of the analytical results, in particular when the analytes are chemical elements.However it is indisputable the usefulness of the chemical analysis of hair for toxicological applications, such as forensics, clinical diagnostics and evaluation of environmental exposure.This paper is focused on the analytical constraints and challenges in quantifying minor and trace elements in hair.The main topics are the characteristics of human hair, the historical evolution of hair chemical analysis, the controversy associated with this type of analysis, and the main advantages and disadvantages of this type of matrix compared with other common biological matrices.A special emphasis is given to hair washing, which is one of the most controversial steps on the analytical procedure.The importance of the validation of analytical systems and the implementation of strategies for results quality assurance and control is also mentioned.

A novel approach is described using chitosan–genipin films as a sustainable method for wine preservation.

Transition-metal complexes have shown significant anti-tumour potential and have advanced towards clinical trials. However, tumour cells often develop resistance to chemotherapeutics, which couple to the inherent compound’s’ toxicity and solubility hampers their translation to the clinics. Therefore, besides the tremendous efforts to synthesise and characterise novel compounds, it is essential to create new drug delivery systems that circumvent these problems, allowing specific and selective delivery of drugs to tumour cells, thus decreasing the required dose and reducing side effects to the healthy tissue. Nano biotechnoloy has been providing for innovative solutions to address this challenge, via the smart design of nano formulations suitable for targeted delivery to the tumour microenvironment. In this review, we discuss recent nano systems combined with medicinal chemistry in cancer therapeutics, focusing on the clinical translation of such systems.

A set of structurally related Ru(η5-C5H5) complexes with bidentate N,N′-heteroaromatic ligands have been evaluated as prospective metallodrugs, with focus on exploring the uptake and cell death mechanisms and potential cellular targets. We have extended these studies to examine the potential of these complexes to target cancer cell metabolism, the energetic-related phenotype of cancer cells. The observations that these complexes can enter cells, probably facilitated by binding to plasma transferrin, and can be retained preferentially at the membranes prompted us to explore possible membrane targets involved in cancer cell metabolism. Most malignant tumors present the Warburg effect, which consists in increasing glycolytic rates with production of lactate, even in the presence of oxygen. The reliance of glycolytic cancer cells on trans-plasma-membrane electron transport (TPMET) systems for their continued survival raises the question of their appropriateness as a target for anticancer drug development strategies. Considering the interesting findings that some anticancer drugs in clinical use are cytotoxic even without entering cells and can inhibit TPMET activity, we investigated whether redox enzyme modulation could be a potential mechanism of action of antitumor ruthenium complexes. The results from this study indicated that ruthenium complexes can inhibit lactate production and TPMET activity in a way dependent on the cancer cell aggressiveness and the concentration of the complex. Combination approaches that target cell metabolism (glycolytic inhibitors) as well as proliferation are needed to successfully cure cancer. This study supports the potential use of some of these ruthenium complexes as adjuvants of glycolytic inhibitors in the treatment of aggressive cancers.

Herein we present the synthesis and characterization of benzo[b]acridin-12(7H)-ones bearing carboranyl moieties and test their biological effectiveness as boron neutron capture therapy (BNCT) agents in cancer treatment. The cellular uptake of these novel compounds into the U87 human glioblastoma cells was evaluated by boron analysis (ICP-MS) and by fluorescence imaging (confocal microscopy). The compounds enter the U87 cells exhibiting a similar profile, i.e., preferential accumulation in the cytoskeleton and membranes and a low cytotoxic activity (IC50 values higher than 200 μM). The cytotoxic activity and cellular morphological alterations after neutron irradiation in the Portuguese Research Reactor (6.6 × 10(7) neutrons cm(-2) s(-1), 1 MW) were evaluated by the MTT assay and by electron microscopy (TEM). Post-neutron irradiation revealed that BNCT has a higher cytotoxic effect on the cells. Accumulation of membranous whorls in the cytoplasm of cells treated with one of the compounds correlates well with the cytotoxic effect induced by radiation. Results provide a strong rationale for considering one of these compounds as a lead candidate for a new generation of BNCT agents.

Global climate change has the potential to seriously and adversely affect marine ecosystem functioning. Numerous experimental and modeling studies have demonstrated how predicted ocean acidification and increased ultraviolet radiation (UVR) can affect marine microbes. However, researchers have largely ignored interactions between ocean acidification, increased UVR and anthropogenic pollutants in marine environments. Such interactions can alter chemical speciation and the bioavailability of several organic and inorganic pollutants with potentially deleterious effects, such as modifying microbial-mediated detoxification processes. Microbes mediate major biogeochemical cycles, providing fundamental ecosystems services such as environmental detoxification and recovery. It is, therefore, important that we understand how predicted changes to oceanic pH, UVR, and temperature will affect microbial pollutant detoxification processes in marine ecosystems. The intrinsic characteristics of microbes, such as their short generation time, small size, and functional role in biogeochemical cycles combined with recent advances in molecular techniques (e.g., metagenomics and metatranscriptomics) make microbes excellent models to evaluate the consequences of various climate change scenarios on detoxification processes in marine ecosystems. In this review, we highlight the importance of microbial microcosm experiments, coupled with high-resolution molecular biology techniques, to provide a critical experimental framework to start understanding how climate change, anthropogenic pollution, and microbiological interactions may affect marine ecosystems in the future.

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 L 2 Pt displays a covalent type of binding, whereas the acridine orange counterpart L 3 Pt shows a combination of intercalative and covalent binding modes with a strong contribution from the former. L 2 Pt 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, L 2 Pt is nine to 27 times more cytotoxic than cisplatin. In the sensitive cell line, L 3 Pt showed a cytotoxic activity similar to that of cisplatin, but like L 2 Pt was able significantly to overcome cisplatin cross‐resistance. Cell‐uptake studies showed that L 2 Pt accumulates preferentially in the cytoplasm, whereas L 3 Pt 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 L 2 Pt because this compound, despite having a weaker ability to target the cell nucleus than L 3 Pt , as well as an inferior DNA affinity, is nevertheless more cytotoxic. Furthermore, ultrastructural studies of A2870 cells exposed to L 2 Pt and L 3 Pt revealed that these complexes induce different alterations in cell morphology, thus indicating the involvement of different modes of action in cell death.

A series of four Pt(II) complexes anchored by bidentate or tridentate pyrazolyl-alkylamine chelators bearing different substituents at the azolyl rings has been prepared with the aim to assess their interest in the design of novel anticancer drugs. All complexes have been fully characterized by classical analytical methods and three of them were characterized also by X-ray diffraction analysis. Their solution behavior, together with lipophilicity measurements, cell uptake, antiproliferative properties, DNA interaction have been evaluated. Albeit all the complexes were less active than cisplatin on ovarian carcinoma A2780 cell line, greatly retained their activity in the cisplatin-resistant A2780cisR cell line and presented a lower resistance factor compared to cisplatin. Moreover, the Pt(II) complexes under investigation were less prone to undergo deactivation by glutathione, believed to be the major cellular target of cisplatin that inactivates the drug by binding to it irreversibly.

An inductively coupled plasma mass spectrometry (ICP-MS) methodology was validated and used for accurately determining the concentration of 17 elements (Al, As, B, Ba, Ca, Co, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, Sr, Zn) in Portuguese wines. This study allowed determining the relationships between element concentration and two variables: wine type (white vs. red) and appellation of origin (“Alentejo”, “Bairrada”, “Dão”, or “Vinho Verde”). Boron made it possible to distinguish among red wines from different producing regions. Factor analysis produced four components (C) with different elements main loading: C1 (the lithophile elements Ba, Mg and Mn); C2 (B, K, and P, elements related to fertilization practices and/or winemaking procedures); C3 (Zn, a metal mainly derived from the use of phytosanitary products and/or stainless steel or brass materials); and C4 (As, mainly derived from phytosanitary products). In total, these components explained 78.1% of the variance between wine type and Appellation. Red wines showed higher scores of C2 than white samples. With respect to the Appellation, “Bairrada” had the highest scores for C2 while “Alentejo” wines, followed by “Dão”, showed highest loadings for C1. Discriminant analysis also achieved a high recognition percentage (98.2%) for the classification of wine samples according to appellation of origin. These results highlight the usefulness of ICP-MS elemental analysis for categorization of wine origin and show that this is a promising technique regarding the authentication of wine certified brand of origin (CBO).

Being mercury one of the most toxic heavy metals present in the environment, it is of major concern to develop cleanup technologies to remove it from wastewater and recover mercury polluted ecosystems. In this context, we study the potential of some microporous titanosilicates and zirconosilicates for taking up Hg2+ from aqueous solutions. These materials have unique chemical and physical properties, and here we are able to confirm that they readily remove Hg2+ from aqueous solutions. Moreover, the presence of the competitive Mg2+ and Na+, which are some of the dominant cations in natural waters, does not reduce the uptake capacity of some of these materials. Thus, several inorganic materials reported here may have important environmental applications, efficiently removing Hg2+ from aqueous solutions.

2+ from aqueous solutions. These materials have unique chemical and physical properties, and here we are able to confirm that they readily remove Hg 2+ from aqueous solutions. Moreover, the presence of the competitive Mg 2+ and Na + , which are some of the dominant cations in natural waters, does not reduce the uptake capacity of some of these materials. Thus, several inorganic materials reported here may have important environmental applications, efficiently removing Hg 2+ from aqueous solutions.