Photophysical properties and quantum chemical studies of poly(2,7-9,9'-dihexylfluorene-dyil)

This work reports the photophysical properties (excitation and fluorescence spectra, fluorescence quantum yield, fluorescence lifetimes) of the poly(2,7-9,9'-dihexylfluorene-dyil) in dilute solutions of four solvents (toluene, tetrahydrofuran, chloroform and ethyl acetate) as well as the properties in solid state. Photoluminescence showed spectra characteristic of disordered α-backbone chain conformation. Simulation of the electronic absorption spectra of oligomers containing 1 to 11 mers showed that the critical conjugation length is between 6 and 7 mers. We also estimated the theoretical dipole moments which indicated that a coil conformation is formed with 8 repeating units per turn. We also showed that some energy transfer process appears in solid state which decreases the emission lifetime. Furthermore, based on luminescent response of the systems herein studied and electroluminescent behavior reported on literature, both photo and electroluminescence emissions arise from the same emissive units.

TiO2-Photocatalyzed degradation of phenol in saline media in an annular reactor: hydrodynamics, lumped kinetics, intermediates, and acute toxicity

The photocatalytic degradation of phenol in aqueous suspensions of TiO2 under different salt concentrations in an annular reactor has been investigated. In all cases, complete removal of phenol and mineralization degrees above 90% were achieved. The reactor operational parameters were optimized and its hydrodynamics characterized in order to couple mass balance equations with kinetic ones. The photodegradation of the organics followed a Langmuir-Hinshelwood-Hougen-Watson lumped kinetics. From GC/MS analyses, several intermediates formed during oxidation have been identified. The main ones were catechol, hydroquinone, and 3-phenyl-2-propenal, in this order. The formation of negligible concentrations of 4-chlorophenol was observed only in high salinity medium. Acute toxicity was determined by using Artemia sp. as the test organism, which indicated that intermediate products were all less toxic than phenol and a significant abatement of the overall toxicity was accomplished, regardless of the salt concentration.

Chemical constituents of the volatile oil from leaves of Annona coriacea and in vitro antiprotozoal activity

The essential oil of the leaves from Annona coriacea Mart., Annonaceae, was extracted by hydrodistillation in a Clevenger apparatus and analyzed by GC/MS and GC/FID. The oil yield was 0.05% m/m. Sixty compounds were identified, in a complex mixture of sesquiterpenes (76.7%), monoterpenes (20.0%) and other constituents (3.3%). Bicyclogermacrene was its major compound (39.8%) followed by other sesquiterpenes. Most of the monoterpenes were in low concentration (<1%). Only β-pinene and pseudolimonene presented the highest level of 1.6%. The volatile oil presented anti-leishmanial and trypanocidal activity against promastigotes of four species of Leishmania and trypomastigotes of Trypanosoma cruzi, showing to be more active against Leishmania (L.) chagasi (IC50 39.93 µ g/mL) (95% CI 28.00-56.95 µ g/mL).

Electrocatalytic oxidation of methanol by the [Ru3O(OAc)6(py)2(CH3OH)]3+cluster: improving the metal-ligand electron transfer by accessing the higher oxidation states of a multicentered system

The [Ru3O(Ac)6(py)2(CH3OH)]+ cluster provides an effective electrocatalytic species for the oxidation of methanol under mild conditions. This complex exhibits characteristic electrochemical waves at -1.02, 0.15 and 1.18 V, associated with the Ru3III,II,II/Ru3III,III,II/Ru 3III,III,III /Ru3IV,III,III successive redox couples, respectively. Above 1.7 V, formation of two RuIV centers enhances the 2-electron oxidation of the methanol ligand yielding formaldehyde, in agreement with the theoretical evolution of the HOMO levels as a function of the oxidation states. This work illustrates an important strategy to improve the efficiency of the oxidation catalysis, by using a multicentered redox catalyst and accessing its multiple higher oxidation states.

Chemical composition and acetylcholinesterase inhibitory activity of essential oils of Myrceugenia myrcioides(Cambess.) O. Berg and Eugenia riedelianaO. Berg, Myrtaceae

The chemical composition of volatile oils from two Myrtaceae species, Myrceugenia myrcioidesand Eugenia riedeliana, both native from the Brazilian Atlantic Rain Forest, was analyzed by GC-MS. Acetylcholinesterase inhibitory activity was colorimetrically evaluated for these oils. For M. myrcioides, monoterpene hydrocarbons represented the major class in the volatile oil, with α-pinene as the most abundant component and a weak inhibitory activity was observed, whilst for E. riedeliana sesquiterpenes were found in higher amounts, being valerianol the major compound, and this oil presented a strong acetylcholinesterase inhibition.

Electrochemical Behavior and Determination of Fluconazole

The electrochemical behavior of fluconazole showed an irreversible oxidation process, with the electrochemical - chemical mechanism being highly dependent on the electrode material. Adsorption of reagent at positive applied potential was observed at Pt electrode while preferential adsorption of the oxidation products was observed at Glassy Carbon surfaces. In pH below 7.0, the anodic current process was intensively decreased. At carbon paste electrode, the fluconazole oxidation current, recorded in phosphate buffer solution (pH 8.0), changed linearly with the fluconazole concentration, Ipa = 5.7×10-5 (mA) × 0.052 [Fluconazol] (μg mL-1), in the range of 48.0 to 250.0 μg mL-1. The detection limit obtained was 6.3 μg mL-1.

Oxidative DNA damage induced by S(IV) in the presence of Cu(II) and Cu(I) complexes

The DNA damage induced by S(IV) in the presence of some Cu(II) complexes in air saturated solution was investigated. The addition of S(IV) to an air saturated solution containing CuII GGA (GGA = glycylglycyl-L-alanine), CuII G3 (G3 = triglycine) or CuII G4 (G4 = tetraglycine) and Ni(II) traces, causes rapid formation of the respective Cu(III) complex, with simultaneous O2 uptake and S(IV) oxidation. SO3•- and HO• were detected by EPR-spin trapping experiments. The DNA strand breaks were attributed to the oxysulfur radicals formed. In the reduction of Cu(II)/BCA (BCA = 4,4' dicarboxy-2-2'-biquinoline) by S(IV), with CuI BCA complex formation, there is the possible formation of carbon centered radical of BCA or peroxyl radical (ROO•) capable of oxidizing DNA bases. The intensity of DNA damage in the presence of these Cu(II) complexes and S(IV) (10-300 µmol L-1) followed the order: CuII BCA ∼ CuII G4 ∼ Cu(II) (added as Cu(NO3)2) > CuII G3 ∼ CuII GGA. Specifically for CuII BCA the damage occurred even at lower S(IV) concentration (0.1 µmol L-1). For the Cu(II) complexes with glycylglycylhistidine, glycylhistidylglycine, glycylhistidyllysine and glycylglycyltyrosylarginine the Cu(III) formation and the DNA damage was not observed.

Electronic conduction and electrocatalysis by supramolecular tetraruthenated copper porphyrazine films

A new tetraruthenated copper(II)-tetra(3,4-pyridyl)porphyrazine species, [CuTRPyPz]4+, has been synthesized and fully characterized by means of analytical, spectroscopic and electrochemical techniques. This À-conjugated system contrasts with the related meso-tetrapyridylporphyrins by exhibiting strong electronic interaction between the coordinated peripheral complexes and the central ring. Based on favorable À-stacking and electrostatic interactions, layer-by-layer assembled films were successfully generated from the appropriate combination of [CuTRPyPz]4+ with copper(II)-tetrasulfonated phtalocyanine, [CuTSPc]4-. Their conducting and electrocatalytic properties were investigated by means of impedance spectroscopy and rotating disc voltammetry, exhibiting metallic behavior near the Ru(III/II) redox potential, as well as enhanced catalytic activity for the oxidation of nitrite and sulphite ions.

Electrochemical and photocatalytic reactions of polycyclic aromatic hydrocarbons investigated by raman spectroscopy

This paper presents the study of photochemical behavior of polycyclic aromatic hydrocarbons (PAHs), potential pollutants in secondary reactions in aerosols, through Raman spectroscopy compared with its electrochemical behavior. The PAHs studied include pyrene, anthracene, phenanthrene and fluorene. These were adsorbed onto TiO2 and irradiated with ultraviolet light (254 nm). Their electrochemical oxidation was studied by in situ Surface-enhanced Raman Scattering (SERS) and led to the formation of carbonyl-containing products. Oxidized intermediates bearing the C=O group were also formed during photodegradation. The joint analysis of the photodegradation data with those produced by electrochemical means - using spectroscopic techniques for the identification and characterization of the products - revealed the formation of identical products for anthracene, but not for pyrene. A reasonable explanation for this difference in results is that photochemical and electrochemical oxidation reactions proceed via different mechanisms. While photocatalytic degradation over TiO2 is initiated by hydroxyl radicals, electrochemical oxidation is initiated by the direct electron transfer from adsorbed PAH to the electrode, generating PAH cation radicals that undergo subsequent reactions.

Energy and amino acid content in phase 1 nursery diet: piglet performance and body chemical composition

It was evaluated the effects of metabolizable energy (ME) and digestible lysine (dLYS) densities on performance and body composition of weaned piglets. The study used 114 piglets weaned at 7.4 ± 0.80 kg, out of which 108 were allotted in the nursery and 6 were slaughtered on the weaning day to determine comparative data of body chemical composition. Six nutrients densities were stipulated from a previous study based on the highest nitrogen retention, maintaining the following ME:LYS relationship in the experimental diets: 3,390:1.291; 3,450:1.409; 3,650:1.411; 3,780:1.461; 3,940:1.507; and 4,109 kcal/kg ME:1.564% dLYS. The experimental diets were offered for 13 days when the piglets reached 12.986 ± 1.449 kg of body weight. The probable residual effects of nutritional density on the subsequent performance of the piglets were evaluated. At the end of initial phase 1, six piglets from each density were slaughtered to determine their chemical composition in body fractions and empty body. There was no significant influence of nutritional levels on the performance of the piglets at the end of the evaluation. The results of food conversion and body composition confirm the level indicated in the previous study, 4 g dLYS/Mcal of ME. The increase of energy and lysine densities confirms the need for a correct relationship among both of them to assure better performance of the piglets at the beginning of the growing phase.

Effect of fructans-based fat replacer on chemical composition, starch digestibility and sensory acceptability of corn snacks

To develop a convenience healthy food snack the partially hydrogenated vegetable fat, used as the flavour fixative agent, was replaced by a non-fat-flavouring solution enriched with inulin and oligofructose. The effects of this replacement on chemical composition, in vitro rate of starch digestion and sensory acceptability were assessed. The new snack presented low-fat levels (0.1 per cent) and around a sevenfold increase in dietary fibre (15.3 per cent of dietary fibre, being 13.3 per cent of fructans) when compared with the traditional ones. The enrichment with fructans reduced the predicted Glycaemic Index by 25 per cent, thus indicating that this dietary fibre contributes effectively towards delaying the in vitro glycaemic response. Fructans-enriched snack presented overall acceptability score (6.6 ± 1.7) similar to the traditional one, flavoured with fatty fixative agent (7.4 ± 1.4). The healthy low-fat fibre-enriched snack produced presented the high sensory acceptability typical for this food product type

Relationship between training status and maximal fat oxidation rate

This study aimed to compare maximal fat oxidation rate parameters between moderate-and low-performance runners. Eighteen runners performed an incremental treadmill test to estimate individual maximal fat oxidation rate (Fat(max)) based on gases measures and a 10,000-m run on a track. The subjects were then divided into a low and moderate performance group using two different criteria: 10,000-m time and VO(2)max values. When groups were divided using 10,000-m time, there was no significant difference in Fat(max) (0.41 +/- 0.16 and 0.27 +/- 0.12 g.min(-1), p = 0.07) or in the exercise intensity that elicited Fat(max) (59.9 +/- 16.5 and 68.7 +/- 10.3 % (V) over dotO(2max), p = 0.23) between the moderate and low performance groups, respectively (p > 0.05). When groups were divided using VO(2max) values, Fat(max) was significantly lower in the low VO(2max) group than in the high VO(2max) group (0.29 +/- 0.10 and 0.47 +/- 0.17 g.min(-1), respectively, p < 0.05) but the intensity that elicited Fat(max) did not differ between groups (64.4 +/- 14.9 and 61.6 +/- 15.4 % VO(2max)). Fat(max) or % VO(2max) that elicited Fat(max) was not associated with 10,000 m time. The only variable associated with 10,000-m running performance was % VO(2max) used during the run (p < 0.01). In conclusion, the criteria used for the division of groups according to training status might influence the identification of differences in Fat(max) or in the intensity that elicits Fat(max).

Study of metal oxide-semiconductor capacitors with rf magnetron sputtering TiO(x) and TiO(x)N(y) gate dielectric layer

Metal oxide-semiconductor capacitors with TiO(x) deposited with different O(2) partial pressures (30%, 35%, and 40%) and annealed at 550, 750, and 1000 degrees C were fabricated and characterized. Fourier transform infrared, x-ray near edge spectroscopy, and elipsometry measurements were performed to characterize the TiO(x) films. TiO(x)N(y) films were also obtained by adding nitrogen to the gaseous mixture and physical results were presented. Capacitance-voltage (1 MHz) and current-voltage measurements were utilized to obtain the effective dielectric constant, effective oxide thickness, leakage current density, and interface quality. The results show that the obtained TiO(x) films present a dielectric constant varying from 40 to 170 and a leakage current density (for V(G)=-1 V, for some structures as low as 1 nA/cm(2), acceptable for complementary metal oxide semiconductor circuits fabrication), indicating that this material is a viable, in terms of leakage current density, highk substitute for current ultrathin dielectric layers. (C) 2009 American Vacuum Society. [DOI: 10.1116/1.3043537]

Heat and chemical stress modulate the expression of the alpha-RYR gene in broiler chickens

The biological cause of Pork Stress syndrome, which leads to PSE (pale, soft, exudative) meat, is excessive release of Ca(2+) ions, which is promoted by a genetic mutation in the ryanodine receptors (RyR) located in the sarcoplasmic reticulum of the skeletal muscle cells. We examined the relationship between the formation of PSE meat under halothane treatment and heat stress exposure in chicken alpha RYR hot spot fragments. Four test groups were compared: 1) birds slaughtered without any treatment, i.e., the control group (C); 2) birds slaughtered immediately after halothane treatment (H); 3) birds slaughtered immediately after heat stress treatment (HS), and 4) birds exposed to halothane and to heat stress (H+HS), before slaughtering. Breast muscle mRNA was extracted, amplified by RT-PCR, and sequenced. PSE meat was evaluated using color determination (L*value). The most common alteration was deletion of a single nucleotide, which generated a premature stop codon, resulting in the production of truncated proteins. The highest incidence of nonsense transcripts came with exposure to halothane; 80% of these abnormal transcripts were detected in H and H+HS groups. As a consequence, the incidence of abnormal meat was highest in the H+HS group (66%). In HS, H, and C groups, PSE meat developed in 60, 50, and 33% of the samples, respectively. Thus, halothane apparently modulates alpha RYR gene expression in this region, and synergically with exposure to heat stress, causes Avian Stress syndrome, resulting in PSE meat in broiler chickens.

Signatures of oxygen on Cu(3)Au(100): From isolated impurity to oxide regimes

We analyze the scanning tunneling microscopy (STM) signatures for the O/Cu(3)Au(100) surface from the low-coverage (isolated impurity) to high-coverage (oxide) regimes. First-principles calculations show that oxygen signatures switch from dark to bright spots as the oxygen coverage increases. This behavior is nicely traced back to a change in the oxygen orbital character of the Fermi-level electronic states. Our results allow for the chemical identification by STM of oxygen and copper atoms in the fully ordered O/Cu(3)Au(100)-c(2x2) surface.