Influence of polyaniline and phthalocyanine hole-transport layers on the electrical performance of light-emitting diodes using MEH-PPV as emissive material

The influence of layer-by-layer films of polyaniline and Ni-tetrasulfonated phthalocyanine (PANI/Ni-TS-Pc) on the electrical performance of polymeric light-emitting diodes (PLED) made from (poly[2-methoxy-5-(2`-ethyl-hexyloxy)-1,4-phenylene vinylene]) (MEH-PPV) is investigated by using current versus voltage measurements and impedance spectroscopy. The PLED is composed by a thin layer of MEH-PPV sandwiched between indium tin oxide (ITO) and aluminum electrodes, resulting in the device structure ITO/(PANI/Ni-TS-Pc)(n)/MEH-PPV/Al, where n stands for the number of PANI/Ni-TS-Pc bilayers. The deposition of PANI/Ni-TS-Pc leads to a decrease in the driving voltage of the PLEDs, which reaches a minimum when n = 5 bilayers. In addition, impedance spectroscopy data reveal that the PLED impedance decreases as more PANI/Ni-TS-Pc bilayers are deposited. The PLED structure is further described by an equivalent circuit composed by two R-C combinations, one for the bulk and other for the interface components, in series with a resistance originated in the ITO contact. From the impedance curves, the values for each circuit element is determined and it is found that both, bulk and interface resistances are decreased upon PANI/Ni-TS-Pc deposition. The results indicate that PANI/NiTS-Pc films reduce the contact resistance at ITO/MEH-PPV interface, and for that reason improve the hole-injection within the PLED structure. (c) 2007 Elsevier B.V. All rights reserved.

Speciation of butyltin derivatives in surface sediments of three southern Brazilian harbors

For the first time, organotin compounds were determined in surface sediment samples collected from Sao Francisco do Sul, Itajai-Navegantes and Imbituba Harbors, located in Santa Catarina State, Brazil. Butyltins (BTs) were determined by gas chromatography with a pulsed flame photometric detector (GC-PFPD) after being modified using the Grignard derivatization method. The concentrations of BTs derivatives ranged from n.d. to 1136.6 ng (Sn) g(-1) of dry weight (dw) sediment for tributyltin (TOT), n.d. to 394.4 ng (Sn)g(-1) dw for dibutyltin (DOT) and n.d. to 312.2 ng (Sn)g(-1) dw for monobutyltin (MBT). The highest concentration of total BTs was found at the Itajai-Acu River dockyard, indicating intense inputs of antifouling paints to the environment. The relative difference in the BTs levels is a particular characteristic of sediments from harbors and may be related to the shipyards and the boat traffic which still use TBT-based antifouling paints.

The effects of conjugated estrogen, raloxifene and soy extract on collagen in rat bones

Objective To evaluate the action of conjugated equine estrogen, raloxifene and isolated or combined genistein-rich soy extracts on collagen fibers in the bones of oophorectomized rats. Materials and methods Seventy female rats received testosterone propionate (0.1 mu g/g) on the 9th day after birth. At 6 months of age, the rats were administered the vehicle (propylene glycol, 0.5 ml/day), and ten of the rats were randomly chosen to comprise the non-oophorectomized control group (GI). The other 60 rats were ovariectomized and randomized into six groups of ten as follows: GII, vehicle; GIII, conjugated equine estrogen (CEE), 50 mu g/kg/day; GIV, raloxifene (RAL), 0.75 mg/kg/day; GV, genistein-rich soy extract (GSE), 300 mg/kg/day; GVI, CEE + GSE, 50 mu g/kg/day + 300 mg/kg/day; and GVII, CEE + RAL, 50 mu g/kg/day + 0.75 mg/kg/day. Three months after surgery, the drugs were administered for 60 consecutive days. All rats were euthanized, and their left tibiae were removed for histological routine. The histological sections were stained with hematoxylin-eosin, and picrosirius for evaluating bone microarchitecture. Types I and II collagen fibers were analyzed by immunofluorescence. Data analysis was carried out with ANOVA and Tukey's test. Results Collagen reduction was significant in the GIII animals when compared to the other groups (p < 0.05). There was no significant difference in the thickness of collagen fibers among the groups. There was a greater quantity of type III collagen in GVI than in the other groups. Conclusion Our data indicate that conjugated equine estrogen improves bone quality because it increases the quantity of type I collagen while reducing the quantity of thin collagen fibers. In addition, the combination of CEE and raloxifene or genistein-rich soy extract is not as efficient as CEE itself to improve bone quality.

Probiotic caprine Coalho cheese naturally enriched in conjugated linoleic acid as a vehicle for Lactobacillus acidophilus and beneficial fatty acids

To obtain a probiotic caprine Coalho cheese naturally enriched in conjugated linoleic acid (CLA), goats' diet was supplemented with soybean oil to produce CLA-enhanced milk, and Lactobacillus acidophilus La5 was incorporated into cheeses. CLA concentration and probiotic viability were evaluated during 60 days. Four pilot-scale cheese-making trials were manufactured, in triplicates. Cheeses T1 and T2 were produced with control milk, and T3 and T4 with CLA-enhanced milk. L. acidophilus was added to cheeses T2 and T4 during processing. The CLA content (isomer C18:2 cis-9, trans-11) in T3 and T4 was 246% to 291% higher than in T1 and T2 (P < 0.01). Populations of L. acidophilus were around 7.5 log cfu g(-1) in T2 and T4 during the study, and the highest CLA content in T4 did not influence the probiotic viability (P > 0.01). The CLA-enriched probiotic caprine Coalho cheese obtained is proposed as a vehicle for beneficial microorganisms and fatty acids. (C) 2012 Elsevier Ltd. All rights reserved.

Gas-phase reactivity of protonated 2-oxazoline derivatives: mass spectrometry and computational studies

RATIONALE: Oxazolines have attracted the attention of researchers worldwide due to their versatility as carboxylic acid protecting groups, chiral auxiliaries, and ligands for asymmetric catalysis. Electrospray ionization tandem mass spectrometric (ESI-MS/MS) analysis of five 2-oxazoline derivatives has been conducted, in order to understand the influence of the side chain on the gas-phase dissociation of these protonated compounds under collision-induced dissociation (CID) conditions. METHODS: Mass spectrometric analyses were conducted in a quadrupole time-of-flight (Q-TOF) spectrometer fitted with electrospray ionization source. Protonation sites have been proposed on the basis of the gas-phase basicity, proton affinity, atomic charges, and a molecular electrostatic potential map obtained on the basis of the quantum chemistry calculations at the B3LYP/6-31 + G(d, p) and G2(MP2) levels. RESULTS: Analysis of the atomic charges, gas-phase basicity and proton affinities values indicates that the nitrogen atom is a possible proton acceptor site. On the basis of these results, two main fragmentation processes have been suggested: one taking place via neutral elimination of the oxazoline moiety (99 u) and another occurring by sequential elimination of neutral fragments with 72 u and 27 u. These processes should lead to formation of R+. CONCLUSIONS: The ESI-MS/MS experiments have shown that the side chain could affect the dissociation mechanism of protonated 2-oxazoline derivatives. For the compound that exhibits a hydroxyl at the lateral chain, water loss has been suggested to happen through an E2-type elimination, in an exothermic step. Copyright (C) 2012 John Wiley & Sons, Ltd.

Conjugated Linoleic Acid Combined with Physical Activity Reduces Body Fat Accumulation But Does Not Modify Lean Body Mass in Male and Female Wistar Rats

Several biological and clinical studies have suggested that conjugated linoleic acid (CLA) prevents body fat accumulation and increases lean body mass. CLA is available as a concentrated dietary supplement and is purported to provide the aforementioned benefits for people who perform physical activity. This study was conducted to evaluate the effect of a CLA-supplemented diet combined with physical activity on the body composition of Wistar rats. Two groups of Wistar rats of both sexes, between 45 and 60 days old, were fed a diet containing 5.5% soybean oil (control group) or a CLA-supplemented diet (0.5% CLA and 5.0% soybean oil) (test group). Half the rats in both groups were assigned to exercise by running on a treadmill. The biochemical and anatomical body compositions were analyzed. In both groups, CLA had no effect on the dietary consumption or the weight of the liver, heart, and lungs. However, it did influence the overall weight gain of exercised male rats and the chemical and anatomical body composition in exercised and sedentary rats of both sexes. The results confirm that a CLA-supplemented diet with and without physical activity reduced body fat accumulation in rats of both sexes. However, there is no evidence of an increase in the lean body mass of the exercised rats.

Novel aryl beta-aminocarbonyl derivatives as inhibitors of Trypanosoma cruzi trypanothione reductase: binding mode revised by docking and GRIND2-based 3D-QSAR procedures

Trypanothione reductase has long been investigated as a promising target for chemotherapeutic intervention in Chagas disease, since it is an enzyme of a unique metabolic pathway that is exclusively present in the pathogen but not in the human host, which has the analog Glutathione reductase. In spite of the present data-set includes a small number of compounds, a combined use of flexible docking, pharmacophore perception, ligand binding site prediction, and Grid-Independent Descriptors GRIND2-based 3D-Quantitative Structure-Activity Relationships (QSAR) procedures allowed us to rationalize the different biological activities of a series of 11 aryl beta-aminocarbonyl derivatives, which are inhibitors of Trypanosoma cruzi trypanothione reductase (TcTR). Three QSAR models were built and validated using different alignments, which are based on docking with the TcTR crystal structure, pharmacophore, and molecular interaction fields. The high statistical significance of the models thus obtained assures the robustness of this second generation of GRIND descriptors here used, which were able to detect the most important residues of such enzyme for binding the aryl beta-aminocarbonyl derivatives, besides to rationalize distances among them. Finally, a revised binding mode has been proposed for our inhibitors and independently supported by the different methodologies here used, allowing further optimization of the lead compounds with such combined structure- and ligand-based approaches in the fight against the Chagas disease.

Fatty acid profile, trans-octadecenoic, alpha-linolenic and conjugated linoleic acid contents differing in certified organic and conventional probiotic fermented milks

Development of dairy organic probiotic fermented products is of great interest as they associate ecological practices and benefits of probiotic bacteria. As organic management practices of cow milk production allow modification of the fatty acid composition of milk (as compared to conventional milk), we studied the influence of the type of milk on some characteristics of fermented milks, such as acidification kinetics. bacterial counts and fatty acid content. Conventional and organic probiotic fermented milks were produced using Bifidobacterium animalis subsp. lactis HN019 in co-culture with Streptococcus thermophilus TA040 and Lactobacillus delbrueckii subsp. bulgaricus LB340. The use of organic milk led to a higher acidification rate and cultivability of Lactobacillus bulgaricus. Fatty acids profile of organic fermented milks showed higher amounts of trans-octadecenoic acid (C18:1, 1.6 times) and polyunsaturated fatty acids, including cis-9 trans-11. C18:2 conjugated linoleic (CLA-1.4 times), and alpha-linolenic acids (ALA-1.6 times), as compared to conventional fermented milks. These higher levels were the result of both initial percentage in the milk and increase during acidification, with no further modification during storage. Finally, use of bifidobacteria slightly increased CLA relative content in the conventional fermented milks, after 7 days of storage at 4 degrees C, whereas no difference was seen in organic fermented milks. (C) 2012 Elsevier Ltd. All rights reserved.

End-to-end Distance Distribution in Fluorescent Derivatives of Bradykinin in Interaction with Lipid Vesicles

Cellular membranes have relevant roles in processes related to proteases like human kallikreins and cathepsins. As enzyme and substrate may interact with cell membranes and associated co-factors, it is important to take into account the behavior of peptide substrates in the lipid environment. In this paper we report an study based on energy transfer in two bradykinin derived peptides labeled with the donor-acceptor pair Abz/Eddnp (ortho-aminobenzoic acid/N-[2,4-dinitrophenyl]-ethylenediamine). Time-resolved fluorescence experiments were performed in phosphate buffer and in the presence of large unilamelar vesicles of phospholipids, and of micelles of sodium dodecyl sulphate (SDS). The decay kinetics were analyzed using the program CONTIN to obtain end-to-end distance distribution functions f(r). Despite of the large difference in the number of residues the end-to-end distance of the longer peptide (9 amino acid residues) is only 20 % larger than the values obtained for the shorter peptide (5 amino acid residues). The proline residue, in position 4 of the bradykinin sequence promotes a turn in the longer peptide chain, shortening its end-to-end distance. The surfactant SDS has a strong disorganizing effect, substantially broadening the distance distributions, while temperature increase has mild effects in the flexibility of the chains, causing small increase in the distribution width. The interaction with phospholipid vesicles stabilizes more compact conformations, decreasing end-to-end distances in the peptides. Anisotropy experiments showed that rotational diffusion was not severely affected by the interaction with the vesicles, suggesting a location for the peptides in the surface region of the bilayer, a result consistent with small effect of lipid phase transition on the peptides conformations.

Theoretical models for the antitrypanosomal activity of thiosemicarbazone derivatives

Thiosemicarbazones are cruzain inhibitors which have been identified as potential antitrypanosomal agents. In this work, several molecular properties were calculated at the density functional theory (DFT)/B3LYP/6-311G* level for a set of 44 thiosemicarbazones. Unsupervised and supervised pattern recognition techniques (hierarchical cluster analysis, principal component analysis, kth-nearest neighbors, and soft independent modeling by class analogy) were used to obtain structureactivity relationship models, which are able to classify unknown compounds according to their activities. The chemometric analyses performed here revealed that 12 descriptors can be considered responsible for the discrimination between high and low activity compounds. Classification models were validated with an external test set, showing that predictive classifications were achieved with the selected variable set. The results obtained here are in good agreement with previous findings from the literature, suggesting that our models can be useful on further investigations on the molecular determinants for the antichagasic activity. (C) 2012 Wiley Periodicals, Inc.

Caco-2 cells cytotoxicity of nifuroxazide derivatives with potential activity against Methicillin-resistant Staphylococcus aureus (MRSA)

It is important to determine the toxicity of compounds and co-solvents that are used in cell monolayer permeability studies to increase confidence in the results obtained from these in vitro experiments. This study was designed to evaluate the cytotoxicity of new nifuroxazide derivatives with potential activity against Methicillin-resistant Staphylococcus aureus (MRSA) in Caco-2 cells to select analogues for further in vitro permeability analyses. In this study, nitrofurantoin and nifuroxazide, in addition to 6 furanic and 6 thiophenic nifuroxazide derivatives were tested at 2, 4, 6, 8 and 10 mu g/mL. In vitro cytotoxicity assays were performed according to the MTT (methyl tetrazolium) assay protocol described in ISO 10993-5. The viability of treated Caco-2 cells was greater than 83% for all tested nitrofurantoin concentrations, while those treated with nifuroxazide at 2, 4 and 6 mu g/mL had viabilities greater than 70%. Treatment with the nifuroxazide analogues resulted in viability values greater than 70% at 2 and 4 mu g/mL with the exception of the thiophenic methyl-substituted derivative, which resulted in cell viabilities below 70% at all tested concentrations. Caco-2 cells demonstrated reasonable viability for all nifuroxazide derivatives, except the thiophenic methyl-substituted compound. The former were selected for further permeability studies using Caco-2 cells. (C) 2012 Elsevier Ltd. All rights reserved.

Credneramides A and B: Neuromodulatory Phenethylamine and Isopentylamine Derivatives of a Vinyl Chloride-Containing Fatty Acid from cf. Trichodesmium sp nov.

Credneramides A (1) and B (2), two vinyl chloride-containing metabolites, were isolated from a Papua New Guinea collection of cf. Trichodesmium sp. nov. and expand a recently described class of vinyl chloride-containing natural products. The precursor fatty acid, credneric acid (3), was isolated from both the aqueous and organic fractions of the parent fraction as well as from another geographically and phylogenetically distinct cyanobacterial collection (Panama). Credneramides A and B inhibited spontaneous calcium oscillations in murine cerebrocortical neurons at low micro-molar concentrations (1, IC50 4.0 mu M; 2, IC50 3.8 mu M).

Preliminary in vitro evaluation of N '-(benzofuroxan-5-yl)methylene benzohydrazide derivatives as potential anti-Trypanosoma cruzi agents

A set of benzofuroxan derivatives was tested in vitro against Trypanosoma cruzi epimastigote forms. The influence of physicochemical properties on these benzofuroxan derivatives' activity was observed, and the presence of electron-withdrawing and hydrophobic groups attached to the benzene ring seems to make a favorable contribution at lower concentrations.

Determination of carrier mobility in MEH-PPV thin-films by stationary and transient current techniques

Charge transport and shelf-degradation of MEH-PPV thin-films were investigated through stationary (e.g. current versus voltage - JxV) and transient (e.g. Time-of-Flight - ToF, Dark-Injection Space-Charge-Limited Current - DI-SCLC, Charge Extraction by Linearly Increasing Voltage - CELN) current techniques. Charge carrier mobility in nanometric films was best characterized through JxV and DI-SCLC. It approaches 10(-6) cm(2)Ns under a SCLC regime with deep traps for light-emitting diode applications. ToF measurements performed on micrometric layers (i.e. - 3 mu m) confirmed studies in 100 nm-thick films as deposited in OLEDs. All results were comparable to a similar poly(para-phenylene vinylene) derivative, MDMO-PPV. Electrical properties extracted from thin-film transistors demonstrated mobility dependence on carrier concentration in the channel (similar to 10(-7)-10(-4) cm(2)/Vs). At low accumulated charge levels and reduced free carrier concentration, a perfect agreement to the previously cited techniques was observed. Degradation was verified through mobility reduction and changes in trap distribution of states. (C) 2011 Elsevier B.V. All rights reserved.

Administration of a murine diet supplemented with conjugated linoleic acid increases the expression and activity of hepatic uncoupling proteins

Daily intake of conjugated linoleic acid (CLA) has been shown to reduce body fat accumulation and to increase body metabolism; this latter effect has been often associated with the up-regulation of uncoupling proteins (UCPs). Here we addressed the effects of a CLA-supplemented murine diet (similar to 2 % CLA mixture, cis-9, trans-10 and trans-10, cis-12 isomers; 45 % of each isomer on alternating days) on mitochondrial energetics, UCP2 expression/activity in the liver and other associated morphological and functional parameters, in C57BL/6 mice. Diet supplementation with CLA reduced both lipid accumulation in adipose tissues and triacylglycerol plasma levels, but did not augment hepatic lipid storage. Livers of mice fed a diet supplemented with CLA showed high UCP2 mRNA levels and the isolated hepatic mitochondria showed indications of UCP activity: in the presence of guanosine diphosphate, the higher stimulation of respiration promoted by linoleic acid in mitochondria from the CLA mice was almost completely reduced to the level of the stimulation from the control mice. Despite the increased generation of reactive oxygen species through oxi-reduction reactions involving NAD(+)/NADH in the Krebs cycle, no oxidative stress was observed in the liver. In addition, in the absence of free fatty acids, basal respiration rates and the phosphorylating efficiency of mitochondria were preserved. These results indicate a beneficial and secure dose of CLA for diet supplementation in mice, which induces UCP2 overexpression and UCP activity in mitochondria while preserving the lipid composition and redox state of the liver.