In vitro and in silico assessment of antitumor properties and biomolecular binding studies for two new complexes based on NiII bearing k2N,S-donor ligands.

This work deals with two new molecule-based materials, namely NiII-complexes of general formulae [Ni(L1)2] (Ni1) and [Ni(L2)2] (Ni2), where L1 = trans-cinnamaldehyde-N(4)-methyl thiosemicarbazone and L2 = trans-cinnamaldehyde-N(4)-ethyl thiosemicarbazone, as potential antitumor agents. Both compounds were characterized by elemental analysis, molar conductivity and spectroscopic techniques (FTIR and NMR). Their molecular structures were obtained by single-crystal X-ray diffraction analysis. Each one crystallizes in a monoclinic space group P 21/c, also the asymmetric unit comprises of one NiII ion located on an inversion centre and one anionic ligand, which acts as a κ2N,S-donor affording a five-membered metallaring. The compounds were screened against two selected tumour cell lines (MCF-7 and A549) and non-tumour fibroblasts cell line (MRC-5) via MTT assays. In both tumour cells, all compounds exhibited higher cytotoxicity than the control drug (cisplatin). The IC50 values ranges of 3.70 - 41.37 µM and 1.06 - 14.91 µM were found for MCF-7 and A549, respectively. Importantly, all of them were less toxicity than cisplatin in MRC-5 with SI values ranged at 11.80 - 86.60. The red blood cell (RBC) assay revealed Ni2 as non-toxic due to its reduced haemolytic effect (0--9% at 1--10 µM). The DNA binding was investigated through a combination of spectrophotometric absorption and emission titrations, electrophoresis, and circular dichroism experiments. As a result, these metal complexes were not able to strongly binding to DNA (Kb values ~104 mol L--1) but suggesting groove-binding interactions. The scavenging ability of them towards 2,2-diphenyl-1-picrylhydrazyl (DPPH) free-radical was also evaluated in this work, but no important antioxidant behaviour was detected. Further, the interaction of Ni1 and Ni2 to human serum albumin (HSA) was explored by quenching of tryptophan emission, warfarin competitive assay, and molecular docking protocols. The HSA binding analyses indicated good affinity of both complexes to Sudlow site I (Kb values ⁓103 mol L-1).

Nanotechnology for catalysis and solar energy conversion.

This roadmap on Nanotechnology for Catalysis and Solar Energy Conversion focuses on the application of nanotechnology in addressing the current challenges of energy conversion: 'high efficiency, stability, safety, and the potential for low-cost/scalable manufacturing' to quote from the contributed article by Nathan Lewis. This roadmap focuses on solar-to-fuel conversion, solar water splitting, solar photovoltaics and bio-catalysis. It includes dye-sensitized solar cells (DSSCs), perovskite solar cells, and organic photovoltaics. Smart engineering of colloidal quantum materials and nanostructured electrodes will improve solar-to-fuel conversion efficiency, as described in the articles by Waiskopf and Banin and Meyer. Semiconductor nanoparticles will also improve solar energy conversion efficiency, as discussed by Boschloo et al in their article on DSSCs. Perovskite solar cells have advanced rapidly in recent years, including new ideas on 2D and 3D hybrid halide perovskites, as described by Spanopoulos et al 'Next generation' solar cells using multiple exciton generation (MEG) from hot carriers, described in the article by Nozik and Beard, could lead to remarkable improvement in photovoltaic efficiency by using quantization effects in semiconductor nanostructures (quantum dots, wires or wells). These challenges will not be met without simultaneous improvement in nanoscale characterization methods. Terahertz spectroscopy, discussed in the article by Milot et al is one example of a method that is overcoming the difficulties associated with nanoscale materials characterization by avoiding electrical contacts to nanoparticles, allowing characterization during device operation, and enabling characterization of a single nanoparticle. Besides experimental advances, computational science is also meeting the challenges of nanomaterials synthesis. The article by Kohlstedt and Schatz discusses the computational frameworks being used to predict structure-property relationships in materials and devices, including machine learning methods, with an emphasis on organic photovoltaics. The contribution by Megarity and Armstrong presents the 'electrochemical leaf' for improvements in electrochemistry and beyond. In addition, biohybrid approaches can take advantage of efficient and specific enzyme catalysts. These articles present the nanoscience and technology at the forefront of renewable energy development that will have significant benefits to society.

The MOD-QM/MM Method: Applications to Studies of Photosystem II and DNA G-Quadruplexes.

Quantum mechanics/molecular mechanics (QM/MM) hybrid methods are currently the most powerful computational tools for studies of structure/function relations and catalytic sites embedded in macrobiomolecules (eg, proteins and nucleic acids). QM/MM methodologies are highly efficient since they implement quantum chemistry methods for modeling only the portion of the system involving bond-breaking/forming processes (QM layer), as influenced by the surrounding molecular environment described in terms of molecular mechanics force fields (MM layer). Some of the limitations of QM/MM methods when polarization effects are not explicitly considered include the approximate treatment of electrostatic interactions between QM and MM layers. Here, we review recent advances in the development of computational protocols that allow for rigorous modeling of electrostatic interactions in biomacromolecules and structural refinement, beyond the common limitations of QM/MM hybrid methods. We focus on photosystem II (PSII) with emphasis on the description of the oxygen-evolving complex (OEC) and its high-resolution extended X-ray absorption fine structure spectra (EXAFS) in conjunction with Monte Carlo structural refinement. Furthermore, we review QM/MM structural refinement studies of DNA G4 quadruplexes with embedded monovalent cations and direct comparisons to NMR data.

Estuarization increases functional diversity of demersal fish assemblages in tropical coastal ecosystems.

This study assessed the influence of the seasonal fluctuation of abiotic conditions (wet v. dry season) on the functional diversity (FD) of tropical coastal fish assemblages. Sampling was carried out in three regions of north-east Brazil with contrasting coastlines (influenced by reef, lagoon and estuary). In each region, fishes were sampled from three depth strata (10, 20 and 30 m) and FD was estimated using an index based on key phenotypic and behavioural characteristics. All three regions had higher FD in the wet season at shallower depths, indicating the coexistence of species with low functional redundancy in sites subject to seasonal flushing of fresh water. Deeper sites had lower FD than shallower sites, although this difference was less pronounced for region 3, which is strongly affected by its proximity to the São Francisco estuary. The results broadly support the hypothesis that alterations in abiotic conditions in the wet season allow estuarine-adapted fishes with a different suite of functional traits to invade shallow coastal regions.

Aqueous extract of Chrysobalanus icaco leaves, in lower doses, prevent fat gain in obese high-fat fed mice.

ETHNOPHARMACOLOGICAL RELEVANCE: Due to the rise in obesity, the necessity for resources and treatments that could reduce the morbidity and mortality associated to this pandemia has emerged. The development of new anti-obesity drugs through herbal sources has been increasing in the past decades which are being used not only as medicine but also as food supplements. Previous studies with the aqueous extract of Chrysobalanus icaco L (AECI) have demonstrated activity on lowering blood glucose levels and body weight. AIM OF THE STUDY: Investigate C. icaco effects in overall adiposity and glycemic homeostasis. MATERIAL AND METHODS: C57BL/6J mice were randomly assigned to standard chow (SC) or high-fat diet (HFD) and treated with AECI in 0.35mg/mL or 0.7mg/mL concentrations ad libitum. Food intake, feed efficiency, metabolic efficiency, body, fat pads and gastrocnemius weight, adiposity index, serum lipids, fecal lipid excretion, locomotor activity in the open field test and insulin and glucose tolerance tests were analyzed and compared. The major components of the extract were demonstrated through HPLC and its antioxidant activity analyzed through DPPH and lipid peroxidation. RESULTS: The AECI in the 0.35mg/mL concentration did not affect food intake or body weight. However, it promoted lower adipose tissue gain, TG levels, and fecal lipid excretion, increased locomotor activity and lean mass weight, and normalized insulin sensitivity and glucose tolerance. Moreover, AECI showed the presence of myricetin 3-O-glucuronide, rutin, quercitrin and myricitrin and demonstrated high-antioxidant activity. CONCLUSIONS: AECI in lower concentrations can prevent fat storage or enhance fat utilization through the increase of locomotor activity. Also, this reinforces its ability to maintain glucose homeostasis through the normalization of insulin sensitivity and glucose tolerance despite the high-fat diet intake. These activities could be associated to the extract's polyphenol content.

Substitution of a hydroxamic acid anchor into the MK-2 dye for enhanced photovoltaic performance and water stability in a DSSC.

An efficient synthetic protocol to functionalize the cyanoacrylic acid anchoring group of commercially available MK-2 dye with a highly water-stable hydroxamate anchoring group is described. Extensive characterization of this hydroxamate-modified dye (MK-2HA) reveals that the modification does not affect its favorable optoelectronic properties. Dye-sensitized solar cells (DSSCs) prepared with the MK-2HA dye attain improved efficiency (6.9%), relative to analogously prepared devices with commercial MK-2 and N719 dyes. The hydroxamate anchoring group also contributes to significantly increased water stability, with a decrease in the rate constant for dye desorption of MK-2HA relative to MK-2 in the presence of water by as much as 37.5%. In addition, the hydroxamate-anchored dye undergoes essentially no loss in DSSC efficiency and the external quantum efficiency improves when up to 20% water is purposefully added to the electrolyte. In contrast, devices prepared with the commercial dye suffer a 50% decline in efficiency under identical conditions, with a concomitant decrease in external quantum efficiency. Collectively, our results indicate that covalent functionalization of organic dyes with hydroxamate anchoring groups is a simple and efficient approach to improving the water stability of the dye-semiconductor interface and overall device durability.

Ecotope effect in Triatoma brasiliensis (Hemiptera: Reduviidae) suggests phenotypic plasticity rather than adaptation.

Triatoma brasiliensis (Hemiptera: Reduviidae) is an important vector of Chagas' disease in both sylvatic and peridomestic ecotopes. Discriminating between these populations of Triatominae has been proposed as a means of investigating re-infestation rates of human dwellings. Geometric morphometrics have been widely applied in the study of Triatominae polymorphisms at species and population levels. This study characterizes morphometric differences between sylvatic and peridomestic populations, as well as between sexes in T. brasiliensis specimens from Jaguaruana, Ceará, in northeastern Brazil. No differences in either the shape or size of the cephalic capsule were apparent between sexes or ecotopes. However, the wings showed differentiation in shape and size. Sexual dimorphism was detected, with females presenting significantly higher values and conformations. Size differentiation was also evident, with sylvatic specimens being generally larger than peridomestic examples. These results indicate that differences in the wings of T. brasiliensis may be related to the existence of phenotypic plasticity, and variations in size and shape may be associated with different ecotopes, possibly as a result of conditions in each micro-habitat, such as temperature, relative humidity, food supply and density.

Fish and aquatic habitat conservation in South America: a continental overview with emphasis on neotropical systems.

Fish conservation in South America is a pressing issue. The biodiversity of fishes, just as with all other groups of plants and animals, is far from fully known. Continuing habitat loss may result in biodiversity losses before full species diversity is known. In this review, the main river basins of South America (Magdalena, Orinoco, Amazon and Paraná-La Plata system), together with key aquatic habitats (mangrove-fringed estuaries of the tropical humid, tropical semi-arid and subtropical regions) are analysed in terms of their characteristics and main concerns. Habitat loss was the main concern identified for all South American ecosystems. It may be caused by damming of rivers, deforestation, water pollution, mining, poor agricultural practice or inadequate management practice. Habitat loss has a direct consequence, which is a decrease in the availability of living resources, a serious social and economic issue, especially for South American nations which are all developing countries. The introduction of exotic species and overfishing were also identified as widespread across the continent and its main freshwater, coastal and marine ecosystems. Finally, suggestions are made to find ways to overcome these problems. The main suggestion is a change of paradigm and a new design for conservation actions, starting with integrated research and aiming at the co-ordinated and harmonized management of the main transboundary waters of the continent. The actions would be focused on habitat conservation and social rescue of the less well-off populations of indigenous and non-indigenous peoples. Energy and freshwater demands will also have to be rescaled in order to control habitat loss.

Spatial and temporal distribution of fishing resources exploited by the Manaus fishing fleet, Amazonas, Brazil

Fishing resources are important generators of income and food for the rural and urban people in the Amazon. The present paper investigates fishing and environmental variables determining fishing production landed in Manaus and evaluates the relative abundance of commercial fishes in the different sub-systems of the Central Amazon basin. Information collected was used to test the new catch index derived from multiple regressions with the following significant variables: number of fisherman days fishing; distance of the fishing ground from Manaus; amount of ice carried during the trip; and river level. There were no significant differences between mean catch values of the Purus, Madeira and Juruá sub-systems. These results suggest that the tributaries of the right margin were very similar and were the most productive in commercial terms. The actual production varies according to the recent magnitude of fishing effort, environmental variations and operational aspects of fishing, particularly ice consumption.

Recursos pesqueiros são importantes fontes de renda e alimento para as populações rurais e urbanas na Amazônia. O presente trabalho avalia a pesca e as variáveis ambientais que determinam a produção de pescarias que desembarcam em Manaus, e avalia também a abundância relativa de recursos pesqueiros em diferentes subsistemas na Amazônia Central. A informação coletada no porto de desembarque de pescado de Manaus foi utilizada para testar um novo índice de captura obtido a partir de um modelo de covariância que apresentou as seguintes variáveis significativas: número de pescadores/dia (dias de pesca vezes número de pescadores por viagem); distância do pesqueiro até Manaus; quantidade de gelo que usou durante a viagem; e nível de rio. Não houve nenhuma diferença significativa entre valores médios de captura entre os subsistemas do Purus, Madeira e de Juruá. Estes resultados sugerem que os tributários da margem direita são similares e mais produtivos em termos comerciais. Concluiu-se que a produção corrente varia de acordo com a magnitude de esforço pesqueiro, por variações ambientais, assim como por aspectos operacionais da pesca, particularmente o consumo de gelo.

Spatial and temporal distribution of fishing resources exploited by the Manaus fishing fleet, Amazonas, Brazil.

Fishing resources are important generators of income and food for the rural and urban people in the Amazon. The present paper investigates fishing and environmental variables determining fishing production landed in Manaus and evaluates the relative abundance of commercial fishes in the different sub-systems of the Central Amazon basin. Information collected was used to test the new catch index derived from multiple regressions with the following significant variables: number of fisherman days fishing; distance of the fishing ground from Manaus; amount of ice carried during the trip; and river level. There were no significant differences between mean catch values of the Purus, Madeira and Juruá sub-systems. These results suggest that the tributaries of the right margin were very similar and were the most productive in commercial terms. The actual production varies according to the recent magnitude of fishing effort, environmental variations and operational aspects of fishing, particularly ice consumption.

Temporal and spatial patterns on serra, Scomberomorus brasiliensis (Teleostei, Scombridae), catches from the fisheries on the Maranhão coast, Brazil.

The displacement pattern of the serra, Scomberomorus brasiliensis, in North-eastern Brazil was analyzed from landing data recorded form the fleet fishing serra. Serra fishery has two seasons: from Septemer to February (demersal species plus serra), and from March to August (almost only large amounts of serra). S. brasilienisis relative abundance increases similarly along the coast from March. but decreases first on the West coast from June. Records indicate that serra is near the coast at least until September/October in Eastern grounds. From October to March (strongest spawning season) there is no record of shoals on the coast. We concluded that the Maranhão coast is just a part of the migration circuit of S. brasilienisis that may exceed 300 nautical miles.