The impact of charge transfer and structural disorder on the thermoelectric properties of cobalt intercalated TiS2

A family of phases, CoxTiS2 (0 ≤ x ≤ 0.75) has been prepared and characterised by powder X-ray and neutron diffraction, electrical and thermal transport property measurements, thermal analysis and SQUID magnetometry. With increasing cobalt content, the structure evolves from a disordered arrangement of cobalt ions in octahedral sites located in the van der Waals’ gap (x ≤ 0.2), through three different ordered vacancy phases, to a second disordered phase at x ≥ 0.67. Powder neutron diffraction reveals that both octahedral and tetrahedral inter-layer sites are occupied in Co0.67TiS2. Charge transfer from the cobalt guest to the TiS2 host affords a systematic tuning of the electrical and thermal transport properties. At low levels of cobalt intercalation (x < 0.1), the charge transfer increases the electrical conductivity sufficiently to offset the concomitant reduction in |S|. This, together with a reduction in the overall thermal conductivity leads to thermoelectric figures of merit that are 25 % higher than that of TiS2, ZT reaching 0.30 at 573 K for CoxTiS2 with 0.04 ≤ x ≤ 0.08. Whilst the electrical conductivity is further increased at higher cobalt contents, the reduction in |S| is more marked due to the higher charge carrier concentration. Furthermore both the charge carrier and lattice contributions to the thermal conductivity are increased in the electrically conductive ordered-vacancy phases, with the result that the thermoelectric performance is significantly degraded. These results illustrate the competition between the effects of charge transfer from guest to host and the disorder generated when cobalt cations are incorporated in the inter-layer space.

Holocene Climatic Optimum centennial-scale paleoceanography in the NE Aegean (Mediterranean sea)

Combined micropaleontological and geochemical analyses of the high-sedimentation gravity core M-4G provided new centennial-scale paleoceanographic data for sapropel S1 deposition in the NE Aegean Sea during the Holocene Climatic Optimum. Sapropel layer S1a (10.2–8.0 ka) was deposited in dysoxic to oxic bottom waters characterized by a high abundance of benthic foraminiferal species tolerating surface sediment and/or pore water oxygen depletion (e.g., Chilostomella mediterranensis, Globobulimina affinis), and the presence of Uvigerina mediterranea, which thrives in oxic mesotrophic-eutrophic environments. Preservation of organic matter (OM) is inferred based on high organic carbon as well as loliolide and isololiolide contents, while the biomarker record and the abundances of eutrophic planktonic foraminifera document enhanced productivity. High inputs of terrigenous OM are attributed to north Aegean borderland riverine inputs. Both alkenone-based sea surface temperatures (SSTs) and δO18G. bulloides records indicate cooling at 8.2 ka (S1a) and ~7.8 ka (S1 interruption). Sapropelic layer S1b (7.7–6.4 ka) is characterized by rather oxic conditions; abundances of foraminiferal species tolerant to oxygen depletion are very low compared with the U. mediterranea rise. Strongly fluctuating SSTs demonstrate repeated cooling and associated dense water formation, with a major event at 7.4 ka followed by cold spells at 7.0, 6.8, and 6.5 ka. The prominent rise of the carbon preference index within the S1b layer indicates the delivery of less degraded terrestrial OM. The increase of algal biomarkers, labile OM-feeding foraminifera and eutrophic planktonic species pinpoints an enhanced in situ marine productivity, promoted by more efficient vertical convection due to repeated cold events. The associated contributions of labile marine OM along with fresher terrestrial OM inputs after ~7.7 ka imply sources alternative/additional to the north Aegean riverine borderland sources for the influx of organic matter in the south Limnos Basin, plausibly related to the inflow of highly productive Marmara/Black Sea waters.

Bond durability in erbium:yttrium-aluminum-garnet laser-irradiated enamel

This study sought to evaluate the influence of thermocycling and water storage on the microtensile bond strength of composite resin bonded to erbium:yttrium-aluminum-garnet (Er:YAG)-irradiated and bur-prepared enamel. Eighty bovine incisors were selected and sectioned. Specimens were ground to produce a flat enamel surface. Samples were randomly assigned according to cavity preparation device: (I) Er:YAG laser and (II) high-speed turbine, and were subsequently restored with composite resin. They were subdivided according to the duration of water storage (WS)/number of thermocycles (TCs): 24 h WS/no TCs; 7 days WS/500 TCs; 1 month WS/2,000 TCs; 6 months WS/12,000 TCs. The teeth were sectioned into 1.0 mm(2)-thick slabs and subjected to tensile stress in a universal testing machine. Data were submitted to two-way analysis of variance (ANOVA) and Tukey`s test at a 0.05 significance level. The different periods of water storage and thermocycling did not influence the microtensile bond strength (A mu TBS) values in the Er:YAG laser-prepared groups. In bur-prepared enamel, the group submitted to 12,000 TCs/6 months` WS (IID) showed a significant decrease in bond strength values when compared to the group stored in water for 24 h and not submitted to thermocycling (IIA), but values were statistically similar to those obtained in all Er:YAG laser groups and in the bur- prepared groups degraded with 500 TCs/1 week WS (IIB) or 2,000 TCs/1 month WS (IIC). It may be concluded that adhesion of an etch-and-rinse adhesive to Er:YAG laser-irradiated enamel was not affected by the methods used to simulate degradation of the adhesive interface and was similar to adhesion in the bur-prepared groups in all periods of water storage and thermocycling.

Expression pattern of four storage xyloglucan mobilization-related genes during seedling development of the rain forest tree Hymenaea courbaril L.

During seedling establishment, cotyledons of the rain forest tree Hymenaea courbaril mobilize storage cell wall xyloglucan to sustain growth. The polysaccharide is degraded and its products are transported to growing sink tissues. Auxin from the shoot controls the level of xyloglucan hydrolytic enzymes. It is not yet known how important the expression of these genes is for the control of storage xyloglucan degradation. In this work, partial cDNAs of the genes xyloglucan transglycosylase hydrolase (HcXTH1) and beta-galactosidase (HcBGAL1), both related to xyloglucan degradation, and two other genes related to sucrose metabolism [alkaline invertase (HcAlkIN1) and sucrose synthase (HcSUS1)], were isolated. The partial sequences were characterized by comparison with sequences available in the literature, and phylogenetic trees were assembled. Gene expression was evaluated at intervals of 6 h during 24 h in cotyledons, hypocotyl, roots, and leaves, using 45-d-old plantlets. HcXTH1 and HcBGAL1 were correlated to xyloglucan degradation and responded to auxin and light, being down-regulated when transport of auxin was prevented by N-1-naphthylphthalamic acid (NPA) and stimulated by constant light. Genes related to sucrose metabolism, HcAlkIN1 and HcSUS1, responded to inhibition of auxin transport in consonance with storage mobilization in the cotyledons. A model is proposed suggesting that auxin and light are involved in the control of the expression of genes related to storage xyloglucan mobilization in seedlings of H. courbaril. It is concluded that gene expression plays a role in the control of the intercommunication system of the source-sink relationship during seeding growth, favouring its establishment in the shaded environment of the rain forest understorey.

Edge effects as the principal cause of area effects on birds in fragmented secondary forest

Bird communities in tropical forests are strongly affected by both patch area and habitat edges. The fact that both effects are intrinsically confounded in space raises questions about how these two widely reported ecological patterns interact, and whether they are independent or simply different spatial manifestations of the same phenomenon. Moreover, do small patches of secondary forest, in landscapes where the most sensitive species have gone locally extinct, exhibit similar patterns to those previously observed in fragmented and continuous primary forests? We addressed these questions by testing edge-related differences in vegetation structure and bird community composition at 31 sites in fragmented and continuous landscapes in the imperilled Atlantic forest of Brazil. Over a two-year period, birds were captured with mist nets to a standardized effort of 680 net-hours at each site (similar to 22 000 net-hours resulting in 3381 captures from 114 species). We found that the bird community in patches of secondary forest was degraded in species composition compared to primary continuous forest, but still exhibited a strong response to edge effects. In fragmented secondary forests, edge and area effects also interacted, such that the magnitude of edge to interior differences on bird community composition declined markedly with patch size. The change in bird species composition between forest interiors and edges was similar to the change in community composition between large and small patches (because species had congruent responses to edge and area), but after controlling for edge effects community composition was no longer affected by patch area. Our results show that although secondary forests hold an impoverished bird community, ecological patterns such as area and edge effects are similar to those reported for primary forests. Our data provide further evidence that edge effects are the main drivers of area effects in fragmented landscapes.

Characterization of Gtf1p, the Connector Subunit of Yeast Mitochondrial tRNA-dependent Amidotransferase

The bacterial GatCAB operon for tRNA-dependent amidotransferase (AdT) catalyzes the transamidation of mischarged glutamyl-tRNA(Gln) to glutaminyl-tRNA(Gln). Here we describe the phenotype of temperature-sensitive (ts) mutants of GTF1, a gene proposed to code for subunit F of mitochondrial AdT in Saccharomyces cerevisiae. The ts gtf1 mutants accumulate an electrophoretic variant of the mitochondrially encoded Cox2p subunit of cytochrome oxidase and an unstable form of the Atp8p subunit of the F(1)-F(0) ATP synthase that is degraded, thereby preventing assembly of the F(0) sector. Allotopic expression of recoded ATP8 and COX2 did not significantly improve growth of gtf1 mutants on respiratory substrates. However, ts gft1 mutants are partially rescued by overexpression of PET112 and HER2 that code for the yeast homologues of the catalytic subunits of bacterial AdT. Additionally, B66, a her2 point mutant has a phenotype similar to that of gtf1 mutants. These results provide genetic support for the essentiality, in vivo, of the GatF subunit of the heterotrimeric AdT that catalyzes formation of glutaminyl-tRNA(Gln) (Frechin, M., Senger, B., Braye, M., Kern, D., Martin, R. P., and Becker, H. D. (2009) Genes Dev. 23, 1119-1130).

Influence of pH on the phototransformation process of PhotogemA (R)

PhotogemA (R) is a hematoporphyrin derivative that has been used as a photosensitizer in experimental and clinical Photodynamic Therapy (PDT) in Brazil. Photosensitizers are degraded under illumination. This process, usually called photobleaching, can be monitored by decreasing in fluorescence intensities and includes the following photoprocesses: photodegradation, phototransformation, and photorelocalization. Photobleaching of hematoporphyrin-type sensitizers during illumination in aqueous solution is related not only to photodegradation but is also followed by the formation of photoproducts with a new fluorescence band at around 640-650 nm and with increased light absorption in the red spectral region at 640 nm. In this study, the influence of pH on the phototransformation process was investigated. PhotogemA (R) solutions, 40 mu g/ml, were irradiated at 514 nm with intensity of 100 mW/cm(2) for 20 min with different pH environments. The controls were performed with the samples in the absence of light. The PhotogemA (R) photodegradation is dependent on the pH. The behavior of photodegradation and photoproducts formation (monitored at 640 nm) is distinct and depends on the photosensitizer concentration. The processes of degradation and photoproducts formation were monitored with Photogemin the concentration of 40 mu g/mL since that demonstrated the best visualization of both processes. While below pH 5 the photodegradation occurred, there was no detectable presence of photoproducts. The increase of pH led to increase of photoproducts formation rate with photodegradation reaching the highest value at pH 10. The increase of photoproducts formation and instability of PhotogemA (R) from pH 6 to pH 10 are in agreement with the desired properties of an ideal photosensitizer since there are significant differences in pH between normal (7.0 < pH < 8.6) and tumor (5.8 < pH < 7.9) tissues. It is important to know the effect of pH in the process of phototransformation (degradation and photoproduct formation) of the molecule since low pH values promotes increase in the proportion of aggregates species in solution and high pH values promotes increase in the proportion of monomeric species. There must be an ideal pH interval which favors the phototransformation process that is correlated with the singlet oxygen formation responsible by the photodynamic effect. These differences in pH between normal and tumor cells can explain the presence of photosensitizers in target tumor cells, making PDT a selective therapy.

Sequential injection analysis (SIA) and response surface methodology: A versatile small volume approach for optimization of photo-Fenton processes

Optimization of photo-Fenton degradation of copper phthalocyanine blue was achieved by response surface methodology (RSM) constructed with the aid of a sequential injection analysis (SIA) system coupled to a homemade photo-reactor. Highest degradation percentage was obtained at the following conditions [H(2)O(2)]/[phthalocyanine] = 7, [H(2)O(2)]/[FeSO(4)] = 10, pH = 2.5, and stopped flow time in the photo reactor = 30 s. The SIA system was designed to prepare a monosegment containing the reagents and sample, to pump it toward the photo-reactor for the specified time and send the products to a flow-through spectrophotometer for monitoring the color reduction of the dye. Changes in parameters such as reagent molar ratios. residence time and pH were made by modifications in the software commanding the SI system, without the need for physical reconfiguration of reagents around the selection valve. The proposed procedure and system fed the statistical program with degradation data for fast construction of response surface plots. After optimization, 97% of the dye was degraded. (C) 2009 Elsevier B.V. All rights reserved.

Applying sequential injection analysis (SIA) and response surface methodology for optimization of Fenton-based processes

This work presents the use of sequential injection analysis (SIA) and the response surface methodology as a tool for optimization of Fenton-based processes. Alizarin red S dye (C.I. 58005) was used as a model compound for the anthraquinones family. whose pigments have a large use in coatings industry. The following factors were considered: [H(2)O(2)]:[Alizarin] and [H(2)O(2)]:[FeSO(4)] ratios and pH. The SIA system was designed to add reagents to the reactor and to perform on-line sampling of the reaction medium, sending the samples to a flow-through spectrophotometer for monitoring the color reduction of the dye. The proposed system fed the statistical program with degradation data for fast construction of response surface plots. After optimization, 99.7% of the dye was degraded and the TOC content was reduced to 35% of the original value. Low reagents consumption and high sampling throughput were the remarkable features of the SIA system. (C) 2008 Published by Elsevier B.V.

Kinetics of autocatalytic acid hydrolysis of cellulose with crystalline and amorphous fractions

The acid hydrolysis of cellulose with crystalline and amorphous fractions is analyzed on the basis of autocatalytic model with a positive feedback of acid production from the degraded biopolymer. In the condition of low acid rate production compared with hydrolysis rate, both fraction of cellulose decrease exponentially with linear and cubic time dependence, and the normalized number of scissions per cellulose chain follows a sigmoid behavior with reaction time. The model predicts that self generated acidic compounds from cellulose accelerate the degradation of the biopolymer. However, if the acidic compounds produced are volatile species, then their release under low pressure will reduce the global rate of degradation of cellulose toward its intrinsic rate value determined by the residual acid catalyst present in the starting material.

Approximate solution of the autocatalytic hydrolysis of cellulose

Depolymerization of cellulose in homogeneous acidic medium is analyzed on the basis of autocatalytic model of hydrolysis with a positive feedback of acid production from the degraded biopolymer. The normalized number of scissions per cellulose chain, S(t)/nA degrees A = 1 - C(t)/C(0), follows a sigmoid behavior with reaction time t, and the cellulose concentration C(t) decreases exponentially with a linear and cubic time dependence, C(t) = C(0)exp[-at - bt (3)], where a and b are model parameters easier determined from data analysis.

Reactivity of Beer Bitter Acids Toward the 1-Hydroxyethyl Radical as Probed by Spin-Trapping Electron Paramagnetic Resonance (EPR) and Electrospray Ionization-Tandem Mass Spectrometry (ESI-MS/MS)

The iso-alpha-acids or isohumulones are the major contributors to the bitter taste of beer, and it is well-recognized that they are degraded during beer aging. In particular, the trans-isohumulones seem to be less stable than the cis-isohumulones. The major radical identified in beer is the 1-hydroxyethyl radical; however, the reactivity between this radical and the isohumulones has not been reported until now. Therefore, we studied the reactivity of isohumulones toward the 1-hydroxyethyl radical through a competitive kinetic approach. It was observed that both cis- and trans-isohumulones and dihydroisohumulones are decomposed in the presence of 1-hydroxyethyl radicals, while the reactivities are comparable. On the other hand, the tetrahydroisohumulones did not react with 1-hydroxyethyl radicals. The apparent second-order rate constants for the reactions between the 1-hydroxyethyl radical and these compounds were determined by electron paramagnetic resonance (EPR) spectroscopy and electrospray ionization-tandem mass spectrometry [ESI(+)-MS/MS]. It follows that degradation of beer bitter acids is highly influenced by the presence of 1-hydroxyethyl radicals. The reaction products were detected by liquid chromatography electrospray ionization-ion trap-tandem mass spectrometry (LC-ESI-IT-MS/MS), and the formation of oxidized derivatives of the isohumulones was confirmed. These data help to understand the mechanism of beer degradation upon aging.

Photocatalytic Decolorization of Commercial Acid Dyes using Solar Irradiation

This work investigates the solar heterogeneous photocatalytic degradation of three commercial acid dyes: Blue 9 (C.I. 42090), Red 51 (C.I. 45430), and Yellow 23 (C.I. 19140). TiO(2) P25 from Degussa was used as the photocatalyst. The dyes were completely degraded within 120 min of treatment in the following increasing order of removal rate: Blue 9 < Yellow 23 < Red 51. The photocatalytic color removal process was well described by a two-first-order in-series reaction, followed by another first-order reaction. Photolytic experiments showed that this process is quite inefficient and highly selective towards Red 51 only. The dyes` solution was completely decolorized and organic matter removals up to 99% were achieved with photocatalysis. The lack of selectivity and the possibility of using solar light to excite the photocatalyst are promising results regarding the feasibility of this technology.

Children's recall of words spoken in their first and second language : Effects of Signal-to-Noise Ratio and Reverberation Time

Speech perception runs smoothly and automatically when there is silence in the background, but when the speech signal is degraded by background noise or by reverberation, effortful cognitive processing is needed to compensate for the signal distortion. Previous research has typically investigated the effects of signal-to-noise ratio (SNR) and reverberation time in isolation, whilst few have looked at their interaction. In this study, we probed how reverberation time and SNR influence recall of words presented in participants' first- (L1) and second-language (L2). A total of 72 children (10 years old) participated in this study. The to-be-recalled wordlists were played back with two different reverberation times (0.3 and 1.2 s) crossed with two different SNRs (+3 dBA and +12 dBA). Children recalled fewer words when the spoken words were presented in L2 in comparison with recall of spoken words presented in L1. Words that were presented with a high SNR (+12 dBA) improved recall compared to a low SNR (+3 dBA). Reverberation time interacted with SNR to the effect that at +12 dB the shorter reverberation time improved recall, but at +3 dB it impaired recall. The effects of the physical sound variables (SNR and reverberation time) did not interact with language. © 2016 Hurtig, Keus van de Poll, Pekkola, Hygge, Ljung and Sörqvist.

Determinação do prazo de validade do medicamento carbocisteína xarope

A carbocisteína é um mucolítico utilizado nos tratamentos sintomáticos das infecções respiratórias, comercializado sem prescrição médica. Cabe ao produtor garantir a qualidade, eficiência e segurança do produto durante o período de validade. A fim de determinar o prazo de validade do produto farmacêutico realizou-se o estudo de estabilidade acelerado, onde através de fatores extrínsecos buscou-se a degradação do fármaco. Arrhenius propôs uma equação através da qual é possível determinar a energia de ativação presente em uma reação química e correlacionou a cinética química à temperatura. O prazo de validade do xarope de carbocisteína foi determinado através da aplicação do método de Arrhenius. A metodologia de análise do produto foi validada quanto a linearidade, precisão, exatidão, limite de detecção, limite de quantificação, robustez e especificidade. Amostras da preparação farmacêutica foram submetidas à degradação térmica nas temperaturas de 40 ºC, 50 ºC, 60 ºC e 70 ºC. A partir dos resultados analíticos aplicou-se a equação de Arrhenius e o método gráfico que determinaram um prazo de validade de 109,28 dias para o produto armazenado em condições ideais de temperatura, a 25 ºC.