Antiplasmodial Drugs in the Gas Phase: A CID and DFT Study of Quinolon-4(1H)-Imine Derivatives

The gas-phase behavior of 12 quinolon-4(1H)-imine derivatives with antiplasmodial activity was investigated using electrospray ionization tandem mass spectrometry together with collision induced dissociation and density functional theory (DFT) calculations. The most probable protonation site was predicted by calculating the proton affinity (PA) values for each possible protonation site and it was found to be the imine nitrogen for all compounds under study. Fragmentation pathways of the protonated molecules were proposed and the assignment of product ion structures was performed taking into account theoretical calculations. The nature of the quinoline substituent was found to influence the gas-phase behavior of the compounds under study. The data acquired allowed to bracket the proton affinity of the quinolin-4-imine scaffold, which can be a useful starting point to choose appropriate references for determining PA values of this scaffold. Figure

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Atmospheric Pressure Plasma Pretreatment of Sugarcane Bagasse: the Influence of Biomass Particle Size in the Ozonation Process

Atmospheric pressure O₂ plasma was used to produce ozone in order to treat sugarcane bagasse as a function of particle sizes. The fixed bagasse moisture content was 50 %. The delignification efficiency had small improvement due to ozonation process as a function of particle size, varying from 75 up to 80 %. Few amounts of hemicellulose were removed, but the ozonation has not been affected significantly with particle size variance as well (from 30 up to 35 %). The cellulose presented some losses below 1.0 mm size (8–15 %) which was an unexpected result. The conversion of cellulose content into free sugar has shown a significant increase as the particle size has diminished as well. The best condition of the bagasse particle size was for 0.08 mm. For this case, a great quantity of cellulose (78.8 %) was converted into glucose. Optical absorption spectroscopy was applied to determine ozone concentrations in real time where the samples with typical bagasse particle sizes equal or below to 0.5 mm had shown a better absorption of ozone in comparison with greater particle size samples.     

Doping Polysulfone Membrane with Alpha‐Tocopherol and Alpha‐Lipoic Acid for Suppressing Oxidative Stress Induced by Hemodialysis Treatment

The reduction of free radicals by bioactive membranes used for hemodialysis treatment is an important topic due to the constant rise of oxidative stress‐associated cardiovascular mortality by hemodialysis patients. Therefore, it is urgent to find an effective solution that helps to solve this problem. Polysulfone membranes enriched with α‐lipoic acid, α‐tocopherol, and with both components are fabricated by spin coating. The antioxidant properties of these membranes are evaluated in vitro by determining the lipid‐peroxidation level and the total antioxidant status of the blood plasma. The biocompatibility is assessed by quantifying the protein adsorption, platelet adhesion, complement activation, and hemolytic effect. All types of membranes show in vitro antioxidant activity and a trend to reduce oxidative stress in vivo; the best results show membranes prepared with a combination of both compounds and prove to be nonhemolytic and hemocompatible. Moreover, the membrane specific separation ability for the main waste products is not affected by antioxidants incorporation.     

Heritability of Stroop and flanker performance in 12-year old children

Background  

There is great interest in appropriate phenotypes that serve as indicator of genetically transmitted frontal (dys)function, such as ADHD. Here we investigate the ability to deal with response conflict, and we ask to what extent performance variation on response interference tasks is caused by genetic variation. We tested a large sample of 12-year old monozygotic and dizygotic twins on two well-known and closely related response interference tasks; the color Stroop task and the Eriksen flanker task. Using structural equation modelling we assessed the heritability of several performance indices derived from those tasks.     

The contribution of high frequencies to human brain activity underlying horizontal localization of natural spatial sounds

Background  

In the field of auditory neuroscience, much research has focused on the neural processes underlying human sound localization. A recent magnetoencephalography (MEG) study investigated localization-related brain activity by measuring the N1m event-related response originating in the auditory cortex. It was found that the dynamic range of the right-hemispheric N1m response, defined as the mean difference in response magnitude between contralateral and ipsilateral stimulation, reflects cortical activity related to the discrimination of horizontal sound direction. Interestingly, the results also suggested that the presence of realistic spectral information within horizontally located spatial sounds resulted in a larger right-hemispheric N1m dynamic range. Spectral cues being predominant at high frequencies, the present study further investigated the issue by removing frequencies from the spatial stimuli with low-pass filtering. This resulted in a stepwise elimination of direction-specific spectral information. Interaural time and level differences were kept constant. The original, unfiltered stimuli were broadband noise signals presented from five frontal horizontal directions and binaurally recorded for eight human subjects with miniature microphones placed in each subject's ear canals. Stimuli were presented to the subjects during MEG registration and in a behavioral listening experiment.     

Tetracyclic Thioxanthene Derivatives: Studies on Fluorescence and Antitumor Activity

Thioxanthones are bioisosteres of the naturally occurring xanthones. They have been described for multiple activities, including antitumor. As such, the synthesis of a library of thioxanthones was pursued, but unexpectedly, four tetracyclic thioxanthenes with a quinazoline–chromene scaffold were obtained. These compounds were studied for their human tumor cell growth inhibition activity, in the cell lines A375-C5, MCF-7 and NCI-H460. Photophysical studies were also performed. Two of the compounds displayed GI₅₀ values below 10 µM for the three tested cell lines, and structure–activity relationship studies were established. Three compounds presented similar wavelengths of absorption and emission, characteristic of dyes with a push-pull character. The structures of two compounds were elucidated by X-ray crystallography. Two tetracyclic thioxanthenes emerged as hit compounds. One of the two compounds accumulated intracellularly as a bright fluorescent dye in the green channel, as analyzed by both fluorescence microscopy and flow cytometry, making it a promising theranostic cancer drug candidate.     

Poly(vinylpyrrolidone)‐based films grown on copper surfaces

The influence of molecular weight and the amount of the poly(vinylpyrrolidone) (PVP) on the growth of poly(vinylpyrrolidone)–based films on copper surfaces was studied by electrochemical, infrared and electronic spectroscopy, and thermogravimetric methods. Complex polymer/metal ions were deposited onto a copper surface, as the result of the electrochemically generated reaction of copper cations with PVP and SCN^?, in sulfuric acid media. Spontaneous film growth on copper surfaces was generated and characterized as a Cu(II)/PVP/SCN^? complex. Infrared spectra and thermal gravimetric curves of the films generated at + 0.7 V were compared with the chemically synthesized complex, and show the same patterns. The oxidation process can be described as: Cu(0)→Cu(I) and Cu(I)→Cu(II), and the copper complex formed at more positive potentials was characterized as Cu(II)/PVP/SCN^?, with copper bonded to the oxygen atom of PVP and thiocyanate ligand N‐linked. This study focuses on the complex formation on a copper surface in acid media and its characterization through electrochemical and spontaneously generated reactions. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2206–2214, 2009     

Finite Element Analysis of Shape Memory Alloy Adaptive Trusses with Geometrical Nonlinearities

This contribution deals with the nonlinear analysis of shape memory alloy (SMA) adaptive trusses employing the finite element method. Geometrical nonlinearities are incorporated into the formulation together with a constitutive model that describes different thermomechanical behaviors of SMA. It has four macroscopic phases (three variants of martensite and an austenitic phase), and considers different material properties for austenitic and martensitic phases together with thermal expansion. An iterative numerical procedure based on the operator split technique is proposed in order to deal with the nonlinearities in the constitutive formulation. This procedure is introduced into ABAQUS as a user material routine. Numerical simulations are carried out illustrating the ability of the developed model to capture the general behavior of shape memory bars. After that, it is analyzed the behavior of some adaptive trusses built with SMA actuators subjected to different thermomechanical loadings.     

Antiproliferative activity, antioxidant capacity and tannin content in plants of semi-arid northeastern Brazil

The objective of this study was to evaluate antiproliferative activity, antioxidant capacity and tannin content in plants from semi-arid northeastern Brazil (Caatinga). For this study, we selected 14 species and we assayed the methanol extracts for antiproliferative activity against the HEp-2 (laryngeal cancer) and NCI-H292 (lung cancer) cell lines using the (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazole) (MTT) method. In addition, the antioxidant activity was evaluated with the DPPH (2,2-diphenyl-2-picrylhydrazyl) assay, and the tannin content was determined by the radial diffusion method. Plants with better antioxidant activity (expressed in a dose able to decrease the initial DPPH concentration by 50%, or IC50) and with higher levels of tannins were: Poincianella pyramidalis (42.95±1.77 μg/mL IC50 and 8.17±0.64 tannin content), Jatropha mollissima (54.09±4.36μg/mL IC50 and 2.35±0.08 tannin content) and Anadenanthera colubrina (73.24±1.47 μg/mL IC50 and 4.41±0.47 tannin content). Plants with enhanced antiproliferative activity (% living cells) were Annona muricata (24.94±0.74 in NCI-H292), Lantana camara (25.8±0.19 in NCI-H292), Handroanthus impetiginosus (41.8±0.47 in NCI-H292) and Mentzelia aspera (45.61±1.94 in HEp-2). For species with better antioxidant and antiproliferative activities, we suggest future in vitro and in vivo comparative studies with other pharmacological models, and to start a process of purification and identification of the possible molecule(s) responsible for the observed pharmacological activity. We believe that the flora of Brazilian semi-arid areas can be a valuable source of plants rich in tannins, cytotoxic compounds and antioxidant agents.     

The Mössbauer spectrum of synthetic hureaulite: Fe5 2+(H2O)4(PO4H)2(PO4)2

The crystal structure of synthetic ferrous hureaulite, Fe₅ ²⁺ (H₂O)₄(PO₄H)₂(PO₄)₂, was refined from single-crystal X-ray data. It is monoclinic, space group C2/c, with a=17.487(4), b=9.017(2), c=9.338(2) Å, β=96.27(3)°, V=1463.6(6) Å³, Z=4 and D _calc=3.327 g/cm³. This end member of the hureaulite series was crystallized under distinctly acidic conditions, by a method that gives perfect crystals, large enough for X-ray single crystal studies. The main feature of the hureaulite structure is that it has an equal number of normal (PO₄)³⁺ and acid (PO₄H)²⁺ tetradentate groups. These are centered on Fe²⁺ atoms and share corners with edge-linked octahedra, forming pentamer units. The five Fe²⁺ atoms are distributed on three distinct sites in these units. This can be directly observed in the Mössbauer spectrum at 295 K, which contains three doublets whose relative intensities correspond to the 1:2:2 distributions of crystallographic sites.