The parallel programming of voluntary and reflexive saccades

A novel two-step paradigm was used to investigate the parallel programming of consecutive, stimulus-elicited ('reflexive') and endogenous ('voluntary') saccades. The mean latency of voluntary saccades, made following the first reflexive saccades in two-step conditions, was significantly reduced compared to that of voluntary saccades made in the single-step control trials. The latency of the first reflexive saccades was modulated by the requirement to make a second saccade: first saccade latency increased when a second voluntary saccade was required in the opposite direction to the first saccade, and decreased when a second saccade was required in the same direction as the first reflexive saccade. A second experiment confirmed the basic effect and also showed that a second reflexive saccade may be programmed in parallel with a first voluntary saccade. The results support the view that voluntary and reflexive saccades can be programmed in parallel on a common motor map. (c) 2006 Elsevier Ltd. All rights reserved.

Rhenium-to-benzoylpyridine and rhenium-to-bipyridine MLCT excited states offac-[Re(Cl)(4-benzoylpyridine)2(CO)3] andfac-[Re(4-benzoylpyridine)(CO)3(bpy)]+: a time-resolved spectroscopic and spectroelectrochemical study

The lowest allowed electronic transition of fac-[Re(Cl)(CO)(3)(bopy)(2)] (bopy = 4-benzoylpyridine) has a Re --> bopy MLCT character, as revealed by UV-vis and stationary resonance Raman spectroscopy. Accordingly, the lowest-lying, long-lived, excited state is Re --> bopy (MLCT)-M-3. Electronic depopulation of the Re(CO)(3) unit and population of a bopy pi* orbital upon excitation are evident by the upward shift of v(Cequivalent toO) vibrations and a downward shift of the ketone v(C=O) vibration, respectively, seen in picosecond time-resolved IR spectra. Moreover, reduction of a single bopy ligand in the (MLCT)-M-3 excited state is indicated by time-resolved visible and resonance Raman (TR3) spectra that show features typical of bopy(.-). In contrast, the lowest allowed electronic transition and lowest-lying excited state of a new complex fac-[Re(bopy)(CO)(3)(bpy)](+) (bpy = 2,2'-bipyridine) have been identified as Re --> bpy MLCT with no involvement of the bopy ligand, despite the fact that the first reduction of this complex is bopy-localized, as was proven spectroelectrochemically. This is a rare case in which the localizations of the lowest MLCT excitation and the first reduction are different. (MLCT)-M-3 excited states of both fac-[Re(Cl)(CO)(3)(bopy)(2)] and fac-[Re(bopy)(CO)(3)(bpy)](+) are initially formed vibrationally hot. Their relaxation is manifested by picosecond dynamic shifts of v(Cequivalent toO) IR bands. The X-ray structure of fac-[Re(bopy)(CO)(3)(bpy)](PF6CH3CN)-C-. has been determined.

Dual-orthogonal radial basis function networks for nonlinear time series prediction

A new structure of Radial Basis Function (RBF) neural network called the Dual-orthogonal RBF Network (DRBF) is introduced for nonlinear time series prediction. The hidden nodes of a conventional RBF network compare the Euclidean distance between the network input vector and the centres, and the node responses are radially symmetrical. But in time series prediction where the system input vectors are lagged system outputs, which are usually highly correlated, the Euclidean distance measure may not be appropriate. The DRBF network modifies the distance metric by introducing a classification function which is based on the estimation data set. Training the DRBF networks consists of two stages. Learning the classification related basis functions and the important input nodes, followed by selecting the regressors and learning the weights of the hidden nodes. In both cases, a forward Orthogonal Least Squares (OLS) selection procedure is applied, initially to select the important input nodes and then to select the important centres. Simulation results of single-step and multi-step ahead predictions over a test data set are included to demonstrate the effectiveness of the new approach.

Replication enhancer elements within the open reading frame of tick-borne encephalitis virus and their evolution within the Flavivirus genus

We provide experimental evidence of a replication enhancer element (REE) within the capsid gene of tick-borne encephalitis virus (TBEV, genus Flavivirus). Thermodynamic and phylogenetic analyses predicted that the REE folds as a long stable stem–loop (designated SL6), conserved among all tick-borne flaviviruses (TBFV). Homologous sequences and potential base pairing were found in the corresponding regions of mosquito-borne flaviviruses, but not in more genetically distant flaviviruses. To investigate the role of SL6, nucleotide substitutions were introduced which changed a conserved hexanucleotide motif, the conformation of the terminal loop and the base-paired dsRNA stacking. Substitutions were made within a TBEV reverse genetic system and recovered mutants were compared for plaque morphology, single-step replication kinetics and cytopathic effect. The greatest phenotypic changes were observed in mutants with a destabilized stem. Point mutations in the conserved hexanucleotide motif of the terminal loop caused moderate virus attenuation. However, all mutants eventually reached the titre of wild-type virus late post-infection. Thus, although not essential for growth in tissue culture, the SL6 REE acts to up-regulate virus replication. We hypothesize that this modulatory role may be important for TBEV survival in nature, where the virus circulates by non-viraemic transmission between infected and non-infected ticks, during co-feeding on local rodents.

Recalcitrant pluralism

Here I argue that the best form of deontology is an ethic of prima facie duties, and that this form of deontology is especially resistant to any form of reduction to a single principle.

Plutarch's 'Lives' and the critical reader

This paper analyses the kind of reader constructed in the Lives and the response expected of that reader. It begins by attempting a typology of moralising in the Lives. Plutarch does sometimes make general 'gnomic' statements about right and wrong, and occasionally passes explicit judgement on a subject's behaviour. In addition, the language with which Plutarch describes character is inherently moralistic; and even when he does not pass explicit judgment, Plutarch can rely on a common set of notions about what makes behaviour virtuous or vicious. However, the application of any moral lessons is left to the reader's own judgement. Furthermore, Plutarch's use of multiple focalisations means that the reader is sometimes presented with varying ways of looking at the same individual or the same historical situation. In addition, many incidents or anecdotes are marked by 'multivalence': that is, they resist reduction to a single moral message or lesson. In such cases, the reader is encouraged to exercise his or her own critical faculties. Indeed, the prologues which precede many pairs of Lives and the synkriseis which follow them sometimes explicitly invite the reader's participation in the work of judging. The syncritic structure of the Parallel Lives also invites the reader's participation, as do the varying perspectives provided by a corpus of overlapping Lives. In fact, the presence of a critical, engaged reader is presupposed by the agonistic nature of much of Greek literature, and of several texts in the Moralia which stage opposing viewpoints or arguments. Plutarch himself argues for such a reader in his How the young man should listen to poems.

Organocatalytic enantioselective construction of nitrocyclohexanes containing multiple chiral centres via a cascade reaction

The stereoselective construction of complex molecules with multiple stereogenicity in a single step represents an extremely useful, but challenging approach to complexity in chemical synthesis. The development of organocatalytic cascade processes has proven useful in these studies, but reports where four or more stereocentres are created in a single step from just two achiral reagents are rare. Herein we report the development of a novel asymmetric domino Michael-Michael reaction between nitrohex-4-enoates and nitro-olefins to generate cyclohexanes of high complexity, including one with a quaternary centre, and one with five contiguous stereocentres. This methodology provides access to a range of useful nitrocyclohexane derivatives, including a novel class of a-lycorane-like structures.

Unusual isotope effect in the reaction of chlorosilylene with trimethylsilane-1-d: Absolute rate studies and quantum chemical and Rice–Ramsperger–Kassel–Marcus calculations provide strong evidence for the involvement of an intermediate complex

Time-resolved studies of chlorosilylene, ClSiH, generated by the 193 nm laser flash photolysis of 1-chloro-1- silacyclopent-3-ene, have been carried out to obtain rate constants for its bimolecular reaction with trimethylsilane-1-d, Me3SiD, in the gas phase. The reaction was studied at total pressures up to 100 Torr (with and without added SF6) over the temperature range of 295−407 K. The rate constants were found to be pressure independent and gave the following Arrhenius equation: log[(k/(cm3 molecule−1 s−1)] = (−13.22 ± 0.15) + [(13.20 ± 1.00) kJ mol−1]/(RT ln 10). When compared with previously published kinetic data for the reaction of ClSiH with Me3SiH, kinetic isotope effects, kD/kH, in the range from 7.4 (297 K) to 6.4 (407 K) were obtained. These far exceed values of 0.4−0.5 estimated for a single-step insertion process. Quantum chemical calculations (G3MP2B3 level) confirm not only the involvement of an intermediate complex, but also the existence of a low-energy internal isomerization pathway which can scramble the D and H atom labels. By means of Rice−Ramsperger−Kassel−Marcus modeling and a necessary (but small) refinement of the energy surface, we have shown that this mechanism can reproduce closely the experimental isotope effects. These findings provide the first experimental evidence for the isomerization pathway and thereby offer the most concrete evidence to date for the existence of intermediate complexes in the insertion reactions of silylenes.

Chemoselective and stereoselective lithium carbenoid mediated cyclopropanation of acyclic allylic alcohols

The reaction of geraniol with different lithium carbenoids generated from n-BuLi and the corresponding dihaloalkane has been evaluated. The reaction occurs in a chemo and stereoselective manner, which is consistent with a directing effect from the oxygen of the allylic moiety. Furthermore, a set of polyenes containing allylic hydroxyl or ether groups were chemoselectively and stereoselectively converted into the corresponding gemdimethylcyclopropanes in one single step in moderate to good yields mediated by a lithium carbenoid generated in situ by reaction of n-BuLi and 2,2-dibromopropane.

Purification, and Biochemical and Biophysical Characterization of Cellobiohydrolase I from Trichoderma harzianum IOC 3844

Because of its elevated cellulolytic activity, the filamentous fungus Trichoderma harzianum has a considerable potential in biomass hydrolysis applications. Trichoderma harzianum cellobiohydrolase I (ThCBHI), an exoglucanase, is an important enzyme in the process of cellulose degradation. Here, we report an easy single-step ion-exchange chromatographic method for purification of ThCBHI and its initial biophysical and biochemical characterization. The ThCBHI produced by induction with microcrystalline cellulose under submerged fermentation was purified on DEAE-Sephadex A-50 media and its identity was confirmed by mass spectrometry. The ThCBHI biochemical characterization showed that the protein has a molecular mass of 66 kDa and pi of 5.23. As confirmed by small-angle X-ray scattering (SAXS), both full-length ThCBHI and its catalytic core domain (CCD) obtained by digestion with papain are monomeric in solution. Secondary structure analysis of ThCBHI by circular dichroism revealed alpha-helices and beta-strands contents in the 28% and 38% range, respectively. The intrinsic fluorescence emission maximum of 337 nm was accounted for as different degrees of exposure of ThCBHI tryptophan residues to water. Moreover, ThCBHI displayed maximum activity at pH 5.0 and temperature of 50 degrees C with specific activities against Avicel and p-nitrophenyl-beta-D-cellobioside of 1.25 U/mg and 1.53 U/mg, respectively.

Approximations of modal logics: K and beyond

Inspired by the recent work on approximations of classical logic, we present a method that approximates several modal logics in a modular way. Our starting point is the limitation of the n-degree of introspection that is allowed, thus generating modal n-logics. The semantics for n-logics is presented, in which formulas are evaluated with respect to paths, and not possible worlds. A tableau-based proof system is presented, n-SST, and soundness and completeness is shown for the approximation of modal logics K, T, D, S4 and S5. (c) 2008 Published by Elsevier B.V.

Extração de boro de água produzida sintética por sistema microemulsionado

Boron is a semi-metal present in certain types of soils and natural waters. It is essential to the healthy development of plants and non-toxic to humans, depending on its concentration. It is used in various industries and it s present in water production coming from oil production. More specifically in Rio Grande do Norte, one of the largest oil producers on shore of Brazil, the relationship water/oil in some fields becomes more than 90%. The most common destination of this produced water is disposal in open sea after processing to meet the legal specification. In this context, this research proposes to study the extraction of boron in water produced by microemulsion systems for industrial utilization. It was taken into account the efficiency of extraction of boron related to surfactant (DDA and OCS, both characterized by FT-IR), cosurfactant (butanol and isoamyl alcohol), organic phase (kerosene and heptanes) and aqueous phase (solution of boron 3.6 ppm in alkaline pH). The ratio cosurfactant/ surfactant used was four and the percentage of organic phases for all points of study was set at 5%. It was chosen points with the highest percentage of aqueous phase. Each system was designed for three points of different compositions in relation to the constituents of a pseudoternary diagram. These points were chosen according to studies of phase behavior in pseudoternary diagrams made in previous studies. For this research, points were chosen in the Winsor II region. The excess aqueous solution obtained in these systems was separated and analyzed by ICP OES. For the data set obtained, the better efficiency in the extraction of boron was obtained using the system with DAC, isoamyl alcohol and heptanes, which extracted 49% in a single step. OCS was not viable to the extraction of boron by microemulsion system in the conditions defined in this study

Niobium Pentachloride Catalyzed Multicomponent Povarov Reaction

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Estudo termoanalítico da perlita hidrofobizada com óleo de linhaça

In this work, expanded perlite, a mineral clay, consisting of SiO2 and Al2O3 in the proportions of 72.1 and 18.5%, respectively, was used as an adsorbent for oil in its pure expanded form as well as hydrofobized with linseed oil. Thermogravimetry (TG), Derivative Thermogravimetry (DTG) and Differential Thermal Analysis (DTA) were used to study the thermal behavior and quantify the percent adsorption of perlite in differents processes comparing the results with the ones obtained using Gravimetric Analysis. In the process of hydrophobization with linseed oil granulometric fractions > 20, 20-32 and 32-60 mesh were used and adsorption tests with crude oil were performed in triplicate at room temperature. The results obtained by TG/DTG in dynamic atmosphere of air showed mass losses in a single step for the expanded perlite with pure adsorbed oil, indicating that the adsorption of oil was limited and that the particle size did not in this process. Linseed oil has performed well as an agent of hydrophobized perlite (32 to 60 mesh) indicating a maximum percentage of 59.9% and 68.6% the linseed with a fraction range from considering the data obtained by thermogravimetry and Gravimetry, respectively. The adsorption of oil in the expanded perlite and hydrofobized pure perlite with linseed oil did not produce good results, characterizing an increase of 0.5 to 4.6% in pure perlite and 3.3% in hydrofobized perlite with granulometric 32 to 60 mesh

Produção de conhecimento sobre narrativas orais: contribuições para as investigações em linguagem infantil

Este estudo tem como objetivo indicar um panorama geral sobre a produção de conhecimento no que tange os padrões para o desenvolvimento da narrativa oral, nos últimos quatro anos por meio de uma revisão bibliográfica sistematizada, voltada para a temática de intervenção em linguagem infantil, com o uso de narrativas orais. A revisão foi realizada em uma única etapa, com critérios específicos, utilizando os seguintes descritores: narrativas, narrativa, narrativas de crianças, linguagem e desenvolvimento, linguagem oral, habilidades linguísticas, linguagem falada, linguagem infantil, narração/narração de histórias e linguagem. O período considerado foi de 2007 a 2011. Foram obtidos 900 registros, dentre os quais, nove (1%) atenderam aos critérios estabelecidos para análise. A maioria dos estudos relacionou-se com análises psicolinguísticas. Apenas um estudo utilizou método experimental. No período considerado foram produzidos poucos estudos abordando narrativas orais infantis; a sua grande maioria levou em consideração, fundamentalmente, aspectos cognitivos e linguísticos no processo de desenvolvimento da habilidade narrativa; a grande maioria das pesquisas foi realizada com crianças que possuem algum tipo de alteração em seu desenvolvimento linguístico. Considera-se que a produção de conhecimento, em relação ao desenvolvimento de narrativas orais infantis, exige, atualmente, um olhar voltado para as intervenções que utilizem metodologia experimental. Por fim, considera-se que é necessária uma atenção maior em relação ao desenvolvimento típico da habilidade narrativa.