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Showing papers by "Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto published in 2016"


Journal ArticleDOI
TL;DR: This review article exploits the most common fragmentation reactions for ions generated by ESI in positive and negative modes using collision cells in an effort to stimulate the use of this technique by non-specialists, undergraduate students and researchers in related areas.

307 citations


Journal ArticleDOI
TL;DR: In this article, the authors examined the impact of the 2010 Amazon drought on forest dynamics using ground-based observations of mortality and growth from an extensive forest plot network and found that during the 2010 drought interval, forests did not gain biomass (net change: −0.43
Abstract: The Amazon Basin has experienced more variable climate over the last decade, with a severe and widespread drought in 2005 causing large basin-wide losses of biomass. A drought of similar climatological magnitude occurred again in 2010; however, there has been no basin-wide ground-based evaluation of effects on vegetation. We examine to what extent the 2010 drought affected forest dynamics using ground-based observations of mortality and growth from an extensive forest plot network. We find that during the 2010 drought interval, forests did not gain biomass (net change: −0.43 Mg ha−1, confidence interval (CI): −1.11, 0.19, n = 97), regardless of whether forests experienced precipitation deficit anomalies. This contrasted with a long-term biomass sink during the baseline pre-2010 drought period (1998 to pre-2010) of 1.33 Mg ha−1 yr−1 (CI: 0.90, 1.74, p < 0.01). The resulting net impact of the 2010 drought (i.e., reversal of the baseline net sink) was −1.95 Mg ha−1 yr−1 (CI:−2.77, −1.18; p < 0.001). This net biomass impact was driven by an increase in biomass mortality (1.45 Mg ha−1 yr−1 CI: 0.66, 2.25, p < 0.001) and a decline in biomass productivity (−0.50 Mg ha−1 yr−1, CI:−0.78, −0.31; p < 0.001). Surprisingly, the magnitude of the losses through tree mortality was unrelated to estimated local precipitation anomalies and was independent of estimated local pre-2010 drought history. Thus, there was no evidence that pre-2010 droughts compounded the effects of the 2010 drought. We detected a systematic basin-wide impact of the 2010 drought on tree growth rates across Amazonia, which was related to the strength of the moisture deficit. This impact differed from the drought event in 2005 which did not affect productivity. Based on these ground data, live biomass in trees and corresponding estimates of live biomass in lianas and roots, we estimate that intact forests in Amazonia were carbon neutral in 2010 (−0.07 Pg C yr−1 CI:−0.42, 0.23), consistent with results from an independent analysis of airborne estimates of land-atmospheric fluxes during 2010. Relative to the long-term mean, the 2010 drought resulted in a reduction in biomass carbon uptake of 1.1 Pg C, compared to 1.6 Pg C for the 2005 event.

183 citations


Journal ArticleDOI
TL;DR: Five new forest free-air CO2 enrichment experiments in mature forests in different biomes and over a wide range of climate space and biodiversity will significantly expand the inference space, and a unique opportunity to initiate a model-data interaction as an integral part of experimental design is presented.
Abstract: The first generation of forest free-air CO2 enrichment (FACE) experiments has successfully provided deeper understanding about how forests respond to an increasing CO2 concentration in the atmosphere. Located in aggrading stands in the temperate zone, they have provided a strong foundation for testing critical assumptions in terrestrial biosphere models that are being used to project future interactions between forest productivity and the atmosphere, despite the limited inference space of these experiments with regards to the range of global ecosystems. Now, a new generation of FACE experiments in mature forests in different biomes and over a wide range of climate space and biodiversity will significantly expand the inference space. These new experiments are: EucFACE in a mature Eucalyptus stand on highly weathered soil in subtropical Australia; AmazonFACE in a highly diverse, primary rainforest in Brazil; BIFoR-FACE in a 150-yr-old deciduous woodland stand in central England; and SwedFACE proposed in a hemiboreal, Pinus sylvestris stand in Sweden. We now have a unique opportunity to initiate a model-data interaction as an integral part of experimental design and to address a set of cross-site science questions on topics including responses of mature forests; interactions with temperature, water stress, and phosphorus limitation; and the influence of biodiversity.

174 citations


Journal ArticleDOI
TL;DR: The one-point method provides a robust means to expand current databases of field-measured Vcmax, giving new potential to improve vegetation models and quantify the environmental drivers of Vc Max variation.
Abstract: Simulations of photosynthesis by terrestrial biosphere models typically need a specification of the maximum carboxylation rate (Vcmax ). Estimating this parameter using A-Ci curves (net photosynthesis, A, vs intercellular CO2 concentration, Ci ) is laborious, which limits availability of Vcmax data. However, many multispecies field datasets include net photosynthetic rate at saturating irradiance and at ambient atmospheric CO2 concentration (Asat ) measurements, from which Vcmax can be extracted using a 'one-point method'. We used a global dataset of A-Ci curves (564 species from 46 field sites, covering a range of plant functional types) to test the validity of an alternative approach to estimate Vcmax from Asat via this 'one-point method'. If leaf respiration during the day (Rday ) is known exactly, Vcmax can be estimated with an r(2) value of 0.98 and a root-mean-squared error (RMSE) of 8.19 μmol m(-2) s(-1) . However, Rday typically must be estimated. Estimating Rday as 1.5% of Vcmax, we found that Vcmax could be estimated with an r(2) of 0.95 and an RMSE of 17.1 μmol m(-2) s(-1) . The one-point method provides a robust means to expand current databases of field-measured Vcmax , giving new potential to improve vegetation models and quantify the environmental drivers of Vcmax variation.

142 citations


Journal ArticleDOI
01 Jul 2016-Talanta
TL;DR: A novel method combining dispersive liquid-liquid microextraction (DLLME) and fast liquid chromatography coupled to mass spectrometry (LC-MS/MS) was developed and validated for the extraction and determination of bisphenol A (BPA) and six bispenol analogues in human urine samples.

88 citations


Journal ArticleDOI
TL;DR: Analytical validation parameters attested that in-tube SPME/UHPLC-MS/MS is an appropriate method to determine parabens in human milk samples to assess human exposure to these compounds.

79 citations


Journal ArticleDOI
TL;DR: The principles, advantages and disadvantages of the disposable pipette tips extraction method are highlighted and recent applications are reviewed.
Abstract: Disposable pipette tips extraction consists of a solid-phase extraction in which the sorbent is poorly dispersed in a pipette tip, which allows a quick and dynamic contact between the aspirated analyte from the sample and the solid phase. It is a technique used particularly in food and forensic analysis, since it requires a small amount of sample and solvent. This article highlights the principles, advantages and disadvantages of the disposable pipette tips extraction method and reviews recent applications.

75 citations


Journal ArticleDOI
TL;DR: The reported high-throughput mitogenomics approach for insects enables new insights into schizophoran diversity and population history of flies.
Abstract: True flies are insects of the order Diptera and encompass one of the most diverse groups of animals on Earth. Within dipterans, Schizophora represents a recent radiation of insects that was used as a model to develop a pipeline for generating complete mitogenomes using various sequencing platforms and strategies. 91 mitogenomes from 32 different species were sequenced and assembled with high fidelity, using amplicon, whole genome shotgun or single molecule sequencing approaches. Based on the novel mitogenomes, we estimate the origin of Schizophora within the Cretaceous-Paleogene (K-Pg) boundary, about 68.3 Ma. Detailed analyses of the blowfly family (Calliphoridae) place its origin at 22 Ma, concomitant with the radiation of grazing mammals. The emergence of ectoparasitism within calliphorids was dated 6.95 Ma for the screwworm fly and 2.3 Ma for the Australian sheep blowfly. Varying population histories were observed for the blowfly Chrysomya megacephala and the housefly Musca domestica samples in our dataset. Whereas blowflies (n = 50) appear to have undergone selective sweeps and/or severe bottlenecks in the New World, houseflies (n = 14) display variation among populations from different zoogeographical zones and low levels of gene flow. The reported high-throughput mitogenomics approach for insects enables new insights into schizophoran diversity and population history of flies.

66 citations


Journal ArticleDOI
TL;DR: In this article, a physical integration of radiometric surface temperature (TR) into an integrated framework of the Penman-Monteith and Shuttleworth-Wallace models was presented to directly quantify the canopy-scale biophysical controls on transpiration (λET) and evaporation (λEE) flux components of the terrestrial latent heat flux.
Abstract: . Canopy and aerodynamic conductances (gC and gA) are two of the key land surface biophysical variables that control the land surface response of land surface schemes in climate models. Their representation is crucial for predicting transpiration (λET) and evaporation (λEE) flux components of the terrestrial latent heat flux (λE), which has important implications for global climate change and water resource management. By physical integration of radiometric surface temperature (TR) into an integrated framework of the Penman–Monteith and Shuttleworth–Wallace models, we present a novel approach to directly quantify the canopy-scale biophysical controls on λET and λEE over multiple plant functional types (PFTs) in the Amazon Basin. Combining data from six LBA (Large-scale Biosphere-Atmosphere Experiment in Amazonia) eddy covariance tower sites and a TR-driven physically based modeling approach, we identified the canopy-scale feedback-response mechanism between gC, λET, and atmospheric vapor pressure deficit (DA), without using any leaf-scale empirical parameterizations for the modeling. The TR-based model shows minor biophysical control on λET during the wet (rainy) seasons where λET becomes predominantly radiation driven and net radiation (RN) determines 75 to 80 % of the variances of λET. However, biophysical control on λET is dramatically increased during the dry seasons, and particularly the 2005 drought year, explaining 50 to 65 % of the variances of λET, and indicates λET to be substantially soil moisture driven during the rainfall deficit phase. Despite substantial differences in gA between forests and pastures, very similar canopy–atmosphere "coupling" was found in these two biomes due to soil moisture-induced decrease in gC in the pasture. This revealed the pragmatic aspect of the TR-driven model behavior that exhibits a high sensitivity of gC to per unit change in wetness as opposed to gA that is marginally sensitive to surface wetness variability. Our results reveal the occurrence of a significant hysteresis between λET and gC during the dry season for the pasture sites, which is attributed to relatively low soil water availability as compared to the rainforests, likely due to differences in rooting depth between the two systems. Evaporation was significantly influenced by gA for all the PFTs and across all wetness conditions. Our analytical framework logically captures the responses of gC and gA to changes in atmospheric radiation, DA, and surface radiometric temperature, and thus appears to be promising for the improvement of existing land–surface–atmosphere exchange parameterizations across a range of spatial scales.

62 citations


Journal ArticleDOI
TL;DR: Differential scanning calorimetry and electron spin resonance data showed that both FPs increase lipid packing and head group ordering as well as reduce the intramembrane water content for anionic membranes, suggesting bending moment in the bilayer could be generated, promoting negative curvature.
Abstract: Viral membrane fusion is an orchestrated process triggered by membrane-anchored viral fusion glycoproteins. The S2 subunit of the spike glycoprotein from severe acute respiratory syndrome (SARS) coronavirus (CoV) contains internal domains called fusion peptides (FP) that play essential roles in virus entry. Although membrane fusion has been broadly studied, there are still major gaps in the molecular details of lipid rearrangements in the bilayer during fusion peptide-membrane interactions. Here we employed differential scanning calorimetry (DSC) and electron spin resonance (ESR) to gather information on the membrane fusion mechanism promoted by two putative SARS FPs. DSC data showed the peptides strongly perturb the structural integrity of anionic vesicles and support the hypothesis that the peptides generate opposing curvature stresses on phosphatidylethanolamine membranes. ESR showed that both FPs increase lipid packing and head group ordering as well as reduce the intramembrane water content for anionic membranes. Therefore, bending moment in the bilayer could be generated, promoting negative curvature. The significance of the ordering effect, membrane dehydration, changes in the curvature properties and the possible role of negatively charged phospholipids in helping to overcome the high kinetic barrier involved in the different stages of the SARS-CoV-mediated membrane fusion are discussed.

59 citations


Journal ArticleDOI
TL;DR: Findings likely underpin physiological effects in a crustacean like M. amazonicum that exploits multiple ecosystems during its life cycle, as well as under culture conditions that may significantly impact shrimp production by the aquaculture industry.

Journal ArticleDOI
TL;DR: In this paper, the Stern-Volmer model was used to investigate the interaction between HSA and trinuclear ruthenium complexes by using fluorescence spectroscopy.

Journal ArticleDOI
TL;DR: In this paper, the growth of CaCO 3 continuous films on Langmuir-Blodgett (LB) modified titanium surfaces and its use as HAp growth inductor was reported.

Journal ArticleDOI
TL;DR: In this article, the performance of the catalysts in a direct ethanol fuel cell (DEFC) was evaluated using cyclic voltammetry and chronoamperometry experiments in acid medium.

Journal ArticleDOI
TL;DR: In this paper, the preparation of heterogeneous catalysts with two different pore sizes, the Fe3O4@nSiO2@MCM-41-MnP and Fe3NSiO 2@mcm-41(E)-mnP catalysts, was reported.

Journal ArticleDOI
TL;DR: In this article, the authors exploited and manipulated the straightforward and fast synthesis method, the so-called "Bromide Anion Exchange" to prepare surfactant-free PdM/C (M = Fe, Mn) nanocatalysts exhibiting unprecedented activity and stability towards ORR.
Abstract: The efficient design of highly active and durable materials towards the ultimate goal of improving kinetics of the oxygen reduction reaction (ORR), which allow enhanced performance in solid alkaline membrane fuel cells (SAMFCs), remains elusive. Seminal studies have shown that by alloying a noble metal such as palladium to a transition metal, it is possible to tune the electronic and/or bifunctional properties enabling substantial ORR performance to be achieved, thereby designing a costly catalyst. Herein, we address and discuss new findings from deeper ORR investigations at palladium-based nanostructures in an alkaline medium. We exploited and manipulated the straightforward and fast synthesis method, the so-called “Bromide Anion Exchange”, to prepare surfactant-free PdM/C (M = Fe, Mn) nanocatalysts exhibiting unprecedented activity and stability towards ORR. PdFe/C from bromide anion exchange (BAE) enables 40- and 4-fold enhancement in terms of exchange current density and kinetic current density and ca. 100 mV gains compared to the polyol microwave-assisted method. After 20 000 cycles of accelerated potential cycling test (APCT), our findings indicate that the present PdM/C bimetallics outperform, to the best of our knowledge, most of the data reported for ORR in alkaline media for Pd-based transition metals. The improved catalytic performances are assigned to the absence of any organic contaminants or protective ligands on their surface and their relatively heterogeneous character comprising nanoalloys and nanowire oxides.

Journal ArticleDOI
TL;DR: The increase in NaOCl concentration and contact time intensified the dissolution of organic matter and dentin collagen with reduction in the amide III/phosphate ratio, which lead to an increase in the tissue dissolution and Dentin collagen deproteination.
Abstract: Sodium hypochlorite (NaOCl) remains the most used irrigation solution during root canal preparation because of characteristics such as wide-spectrum antimicrobial activity and organic tissue dissolution capacity. However, these solutions can alter dentin composition and there is no consensus on the optimal concentration of NaOCl to be used. Objectives To determine the organic matter dissolution and changes in dentin chemical composition promoted by different concentrations of NaOCl over time. Material and Methods: Fragments of bovine muscle tissue were weighed before and after 5, 10, and 15 min of immersion in the groups (n=10): G1- 0.9% saline solution; G2- 1% NaOCl; G3- 2.5% NaOCl; and G4- 5% NaOCl. Bovine dentin fragments were subjected to the same irrigants and absorption spectra were collected by Attenuated Total Reflectance of Fourier Transform Infrared Spectroscopy (ATR-FTIR) before and after 0,5, 1, 2, 3, 5, 8, and 10 min of immersion in the solutions. The ratios of the amide III/phosphate and carbonate/phosphate absorption bands were determined. The tissue dissolution and carbonate/phosphate ratios were submitted to the two-way analysis of variance (ANOVA) with Tukey’s multiple-comparison test (α 0.05). Intergroup differences were not observed in this ratio (p>0.05). Conclusions The increase in the exposure time and in the concentration of NaOCl solution lead to an increase in the tissue dissolution and dentin collagen deproteination. Furthermore, some carbonate ions are removed from the dentin inorganic phase by the NaOCl.

Journal ArticleDOI
TL;DR: The results indicated that C. tropicalis is susceptible to treatment with PG-EO, geraniol, and linalool, which could become options to prevent or treat this infection.
Abstract: Dental prosthesis supports Candida species growth and may predispose the oral cavity to lesions. C. tropicalis has emerged as a colonizer of prosthesis and has shown resistance to clinically used antifungal agents, which has increased the search for new antifungals. This work describes the effectiveness of fifteen essential oils (EOs) against C. tropicalis The EOs were obtained by hydrodistillation and were chemically characterized by gas chromatography-mass spectrometry. The antifungal activities of the EOs were evaluated by the microdilution method and showed that Pelargonium graveolens (Geraniaceae) (PG-EO) was the most effective oil. Geraniol and linalool were the major constituents of PG-EO. The 2,3-Bis-(2-Methoxy-4-Nitro-5-Sulfophenyl)-2H-Tetrazolium-5-Carboxanilide (XTT) assay showed that all the clinical C. tropicalis strains formed viable biofilms. Scanning electron microscopy examination of the biofilms revealed a complex architecture with basal layer of yeast cells and an upper layer of filamentous cells. Treatments with PG-EO, linalool, and geraniol significantly reduced the number of viable biofilm cells and inhibited biofilm formation after exposure for 48 h. PG-EO, geraniol, and linalool were not toxic to normal human lung fibroblasts (GM07492A) at the concentrations they were active against C. tropicalis Together, our results indicated that C. tropicalis is susceptible to treatment with PG-EO, geraniol, and linalool, which could become options to prevent or treat this infection.

Journal ArticleDOI
TL;DR: Analysis of 2-Cys Prx structures in the fully folded (but not locally unfolded) form revealed a highly conserved, non-conventional hydrogen bond between the catalytic triad Thr of a dimer with an aromatic residue of an adjacent dimer.
Abstract: Typical 2-Cys Peroxiredoxins (2-Cys Prxs) reduce hydroperoxides with extraordinary rates due to an active site composed of a catalytic triad, containing a peroxidatic cysteine (CP), an Arg, and a Thr (or Ser). 2-Cys Prx are involved in processes such as cancer; neurodegeneration and host-pathogen interactions. During catalysis, 2-Cys Prxs switch between decamers and dimers. Analysis of 2-Cys Prx structures in the fully folded (but not locally unfolded) form revealed a highly conserved, non-conventional hydrogen bond (CH-π) between the catalytic triad Thr of a dimer with an aromatic residue of an adjacent dimer. In contrast, structures of 2-Cys Prxs with a Ser in place of the Thr do not display this CH-π bond. Chromatographic and structural data indicate that the Thr (but not Ser) destabilizes the decamer structure in the oxidized state probably through steric hindrance. As a general trend, mutations in a yeast 2-Cys Prx (Tsa1) favoring the dimeric state also displayed a decreased catalytic activity. Remarkably, yeast naturally contains Thr-Ser variants (Tsa1 and Tsa2, respectively) with distinct oligomeric stabilities in their disulfide states.

Journal ArticleDOI
TL;DR: In vitro APT of the plant-pathogenic fungus Colletotrichum acutatum with furocoumarins and coumarin and solar radiation was investigated, finding 8-MOP was the most effective treatment and no damage to sweet orange leaves was observed after APT with any of the compounds or extracts.
Abstract: The increasing tolerance to currently used fungicides and the need for environmentally friendly antimicrobial approaches have stimulated the development of novel strategies to control plant-pathogenic fungi such as antimicrobial phototreatment (APT). We investigated the in vitro APT of the plant-pathogenic fungus Colletotrichum acutatum with furocoumarins and coumarins and solar radiation. The compounds used were: furocoumarins 8-methoxypsoralen (8-MOP) and 5,8-dimethoxypsoralen (isopimpinellin), coumarins 2H-chromen-2-one (coumarin), 7-hydroxycoumarin, 5,7-dimethoxycoumarin (citropten) and a mixture (3:1) of 7-methoxycoumarin and 5,7-dimethoxycoumarin. APT of conidia with crude extracts from 'Tahiti' acid lime, red and white grapefruit were also performed. Pure compounds were tested at 50μM concentration and mixtures and extracts at 12.5mgL(-1). The C. acutatum conidia suspension with or without the compounds was exposed to solar radiation for 1h. In addition, the effects of APT on the leaves of the plant host Citrus sinensis were determined. APT with 8-MOP was the most effective treatment, killing 100% of the conidia followed by the mixture of two coumarins and isopimpinellin that killed 99% and 64% of the conidia, respectively. APT with the extracts killed from 20% to 70% of the conidia, and the extract from 'Tahiti' lime was the most effective. No damage to sweet orange leaves was observed after APT with any of the compounds or extracts.

Journal ArticleDOI
TL;DR: It is suggested that H shrimp utilise a camouflage strategy specialised to a limited number of backgrounds at any one time, whereas ST individuals comprise a phenotype with more generalist camouflage (transparency) linked to a more generalists background utilisation.
Abstract: Colour and shape polymorphisms are important features of many species and may allow individuals to exploit a wider array of habitats, including through behavioural differences among morphs. In addition, differences among individuals in behaviour and morphology may reflect different strategies, for example utilising different approaches to camouflage. Hippolyte obliquimanus is a small shrimp species inhabiting different shallow-water vegetated habitats. Populations comprise two main morphs: homogeneous shrimp of variable colour (H) and transparent individuals with coloured stripes (ST). These morphs follow different distribution patterns between their main algal habitats; the brown weed Sargassum furcatum and the pink-red weed Galaxaura marginata. In this study, we first investigated morph-specific colour change and habitat selection, as mechanisms underlying camouflage and spatial distribution patterns in nature. Then, we examined habitat fidelity, mobility, and morphological traits, further indicating patterns of habitat use. H shrimp are capable of changing colour in just a few days towards their algal background, achieving better concealment in the more marginal, and less preferred, red weed habitat. Furthermore, laboratory trials showed that habitat fidelity is higher for H shrimp, whereas swimming activity is higher for the ST morph, aligned to morphological evidence indicating these two morphs comprise a more benthic (H) and a more pelagic (ST) life-style, respectively. Results suggest that H shrimp utilise a camouflage strategy specialised to a limited number of backgrounds at any one time, whereas ST individuals comprise a phenotype with more generalist camouflage (transparency) linked to a more generalist background utilisation. The coexistence within a population of distinct morphotypes with apparently alternative strategies of habitat use and camouflage may reflect differential responses to substantial seasonal changes in macroalgal cover. Our findings also demonstrate how colour change, behaviour, morphology, and background use all interact in achieving camouflage.

Journal ArticleDOI
TL;DR: Combining camera trap data with an open-robust design mark–recapture model to estimate the number of dogs that used protected areas in Brazilian Atlantic Forest provides important demographic information on free-ranging dogs that can guide management strategies to directly control dogs' abundance and ranging behavior.
Abstract: Worldwide, domestic dogs (Canis familiaris) are one of the most common carnivoran species in natural areas and their populations are still increasing. Dogs have been shown to impact wildlife populations negatively, and their occurrence can alter the abundance, behavior, and activity patterns of native species. However, little is known about abundance and density of the free-ranging dogs that use protected areas. Here, we used camera trap data with an open-robust design mark–recapture model to estimate the number of dogs that used protected areas in Brazilian Atlantic Forest. We estimated the time period these dogs used the protected areas, and explored factors that influenced the probability of continued use (e.g., season, mammal richness, proportion of forest), while accounting for variation in detection probability. Dogs in the studied system were categorized as rural free-ranging, and their abundance varied widely across protected areas (0–73 individuals). Dogs used protected areas near human houses for longer periods (e.g., >50% of sampling occasions) compared to more distant areas. We found no evidence that their probability of continued use varied with season or mammal richness. Dog detection probability decreased linearly among occasions, possibly due to the owners confining their dogs after becoming aware of our presence. Comparing our estimates to those for native carnivoran, we found that dogs were three to 85 times more abundant than ocelots (Leopardus pardalis), two to 25 times more abundant than puma (Puma concolor), and approximately five times more abundant than the crab-eating fox (Cerdocyon thous). Combining camera trapping data with modern mark–recapture methods provides important demographic information on free-ranging dogs that can guide management strategies to directly control dogs' abundance and ranging behavior.

Journal ArticleDOI
TL;DR: The results are relevant to understanding the behavior and use of aluminum chloride phthalocyanine in the design of new drug delivery systems for clinical application in photodynamic therapy as a new approach to treat skin cancer.

Journal ArticleDOI
TL;DR: Principal component analysis (PCA) and partial least squares (PLS) indicated that the data dimension could be reduced and that TAN, SCOD, DOC and nitrification efficiency were the main variables that affected the performance of the AS reactors.

Journal ArticleDOI
TL;DR: Molecular dynamics simulations using the OPEP coarse-grained force field for proteins show that the mutant E17Q is subject to larger structural fluctuations when compared to the wild type, and can contribute to the design of new mutants with specific association properties.
Abstract: Spider silk is a fascinating material combining mechanical properties such as maximum strength and high toughness comparable or better than man-made materials, with biocompatible degradability characteristics. Experimental measurements have shown that pH triggers the dimer formation of the N-terminal domain (NTD) of the major ampullate spidroin 1 (MaSp 1). A coarse-grained model accounting for electrostatics, van der Waals and pH-dependent charge-fluctuation interactions, by means of Monte Carlo simulations, gave us a more comprehensive view of the NTD dimerization process. A detailed analysis of the electrostatic properties and free energy derivatives for the NTD homoassociation was carried out at different pH values and salt concentrations for the protein wild type and for several mutants. We observed an enhancement of dipole–dipole interactions at pH 6 due to the ionization of key amino acids, a process identified as the main driving force for dimerization. Analytical estimates based on the DVLO theory framework corroborate our findings. Molecular dynamics simulations using the OPEP coarse-grained force field for proteins show that the mutant E17Q is subject to larger structural fluctuations when compared to the wild type. Estimates of the association rate constants for this mutant were evaluated by the Debye–Smoluchowski theory and are in agreement with the experimental data when thermally relaxed structures are used instead of the crystallographic data. Our results can contribute to the design of new mutants with specific association properties.

Journal ArticleDOI
TL;DR: Kinetic assays and molecular modeling studies confirm that these compounds block both catalytic and peripheral AChE sites, which is quite interesting since the triazole-quinoline system is a new structural scaffold for A ChE inhibitors.
Abstract: Alzheimer’s disease (AD) is the most prevalent neurodegenerative disorder worldwide. Currently, the only strategy for palliative treatment of AD is to inhibit acetylcholinesterase (AChE) in order to increase the concentration of acetylcholine in the synaptic cleft. Evidence indicates that AChE also interacts with the β-amyloid (Aβ) protein, acting as a chaperone and increasing the number and neurotoxicity of Aβ fibrils. It is known that AChE has two binding sites: the peripheral site, responsible for the interactions with Aβ, and the catalytic site, related with acetylcholine hydrolysis. In this work, we reported the synthesis and biological evaluation of a library of new tacrine-donepezil hybrids, as a potential dual binding site AChE inhibitor, containing a triazole-quinoline system. The synthesis of hybrids was performed in four steps using the click chemistry strategy. These compounds were evaluated as hAChE and hBChE inhibitors, and some derivatives showed IC50 values in the micro-molar range and were remarkably selective towards hAChE. Kinetic assays and molecular modeling studies confirm that these compounds block both catalytic and peripheral AChE sites. These results are quite interesting since the triazole-quinoline system is a new structural scaffold for AChE inhibitors. Furthermore, the synthetic approach is very efficient for the preparation of target compounds, allowing a further fruitful new chemical library optimization.

Journal ArticleDOI
TL;DR: It is demonstrated that AlClPc self-aggregation occurred even in the liposomes, and this amazing behavior is new and increases the scientific knowledge about the intracellular mechanism of action of PDT photosensitizers.
Abstract: Aluminum phthalocyanine chloride (AlClPc) is a second-generation photodynamic therapy (PDT) photosensitizer characterized for its high hydrophobicity and self-aggregation tendency in aqueous media, which hamper its potential application. Aiming at AlClPc solubilization we proposed here the use of 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC) and 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) at different proportions to form mixed lipid vesicles (LVs) as a drug delivery system. LVs were prepared by ethanol injection method and formed nano-sized vesicles (about 100nm) with suitable polydispersity index, negative zeta potential, and stable in aqueous medium for at least 50days. AlClPc strongly interacts with LV (high binding constant values), especially due to aluminum-phosphate specific interactions, which gives a surface localization to AlClPc molecules as demonstrated by fluorescence quenching data. Anisotropy, static and time-resolved fluorescence measurements corroborated with these results and demonstrated that AlClPc self-aggregation occurred even in the liposomes. However, formulation uptake by oral squamous cell carcinoma (OSCC) the AlClPc was distributed in cellular organelles and suffered a disaggregation process demonstrated by fluorescence life-time imaging microscopy. This amazing behavior is new and increases the scientific knowledge about the intracellular mechanism of action of PDT photosensitizers. In addition, these results open a new perspective to the potential use of AlClPc-LV formulations for photodynamic treatment.

Journal ArticleDOI
TL;DR: In this article, structural and spectroscopic properties of Nb 2 O 5 nanocrystalline powders were investigated using the sol-gel method. And the results showed that the synthetized materials can find widespread applicability in photonics as red luminophor for white LED, optical amplifiers and upconverter materials.

Journal ArticleDOI
TL;DR: Using RNA interference approaches, it is found that the gene Sex combs reduced (Scr) determines the wingless identity of T1 in the cockroach Blattella germanica, and this data support the theory of a dual origin for insect wings.
Abstract: Wings were a fundamental morphological innovation for the adaptive radiation of insects, the most diversified group among all animals. Pterygote insects have two pairs of wings, the mesothoracic (T...

Journal ArticleDOI
TL;DR: In this article, the authors used camera-trap data, occupancy models, and temporal overlap indexes to explore whether ocelot occurrence influenced the habitat use or activity patterns of 6 mesocarnivores in reserves of the Brazilian Atlantic Forest.
Abstract: Fragmentation and habitat loss are top threats to tropical forest biodiversity and the Atlantic Forest is no exception. Over 80% of Atlantic Forest remnants in Brazil are < 50 ha and lack resident populations of large predators (jaguars, Panthera onca , and pumas, Puma concolor ). Mesopredators with opportunistic life-history characteristics (e.g., ocelots, Leopardus pardalis ) are now hypothesized to be the dominant competitor(s) in these systems and may negatively affect the spatial or temporal distribution of other sympatric mesocarnivores. We used camera-trap data, occupancy models, and temporal overlap indexes to explore whether ocelot occurrence influenced the habitat use or activity patterns of 6 mesocarnivores in reserves of the Brazilian Atlantic Forest. Ocelot occurrence did not influence the habitat use of these mesocarnivores. Moreover, the ability of some mesocarnivore species, especially the little spotted cat ( L. guttulus ), to adjust their activity patterns to avoid direct contact with ocelots may facilitate their coexistence in these Atlantic Forest remnants. Ocelot occurrence did not influence the activity pattern of 2 nocturnal species (the crab-eating fox, Cerdocyon thous , and the crab-eating raccoon, Procyon cancrivorus ), suggesting that these species are more tolerant of ocelots than other mesocarnivores. The probability of occupancy varied among species, with tayra ( Eira barbara ) and South American coati ( Nasua nasua ) having the highest occupancy estimates; overall, occupancy by mesocarnivores correlated negatively with reserve size. Because mesocarnivores are important drivers of ecosystem function, structure, and dynamics and may occupy unique roles that cannot be filled by larger carnivores, future studies should assess environmental factors influencing the use of these small remnants of Atlantic Forest by each mesocarnivore species. A fragmentacao e a perda de habitat sao as principais ameacas para a biodiversidade da floresta tropical e a Mata Atlântica nao e excecao. Mais de 80% dos remanescentes de Mata Atlântica no Brasil sao < 50 ha e nao tem populacoes residentes de grandes predadores (oncas-pintadas, Panthera onca , e oncas-pardas, Puma concolor ). Uma hipotese atual indica que mesopredadores com caracteristicas oportunistas de historia de vida (ex., jaguatiricas, Leopardus pardalis ) sao os competidores dominantes nestes sistemas, podendo afetar negativamente a distribuicao espacial ou temporal de outros mesocarnivoros simpatricos. Nos utilizamos dados de armadilhas fotograficas, modelos de ocupacao e indices de sobreposicao temporal para explorar se a ocorrencia da jaguatirica influencia o uso do habitat ou o padrao de atividade de 6 mesocarnivoros em reservas da Mata Atlântica brasileira. Nossos resultados indicam que a ocorrencia da jaguatirica nao influenciou o uso do habitat por estes mesocarnivoros. Alem disso, a capacidade de algumas especies de mesocarnivoros, especialmente o gato-do-mato ( L. guttulus ), de ajustar os seus padroes de atividade para evitar um contato direto com as jaguatiricas pode facilitar a coexistencia destas especies nestes remanescentes de Mata Atlântica. A ocorrencia da jaguatirica nao influenciou o padrao de atividade de 2 especies noturnas (o cachorro-do-mato, Cerdocyon thous , e o mao-pelada, Procyon cancrivorus ), sugerindo que estas especies sao mais tolerantes a jaguatirica que outros mesocarnivoros. A probabilidade de ocupacao variou entre as especies, com a irara ( Eira barbara ) e o quati sul americano ( Nasua nasua ) apresentando as estimativas mais altas de ocupacao. No geral, a ocupacao do habitat pelos mesocarnivoros correlacionou negativamente com o tamanho da reserva. Visto que os mesocarnivoros sao importantes direcionadores da funcao, da estrutura e das dinâmicas do ecossistema e podem ocupar papeis unicos que nao podem ser preenchidos por carnivoros maiores, estudos futuros devem avaliar os fatores ambientais que estao infuenciando o uso destes pequenos remanescentes de Mata Atlântica por cada especie de mesocarnivoro.