Solution structure of CnErg1 (Ergtoxin), a HERG specific scorpion toxin

The three-dimensional structure of chemically synthesized CnErg1 (Ergtoxin), which specifically blocks HERG (human ether-a-go-go-related gene) K+ channels, was determined by nuclear magnetic resonance spectroscopy. CnErg1 consists of a triple-stranded beta-sheet and an a-helix, as is typical of K+ channel scorpion toxins. The peptide structure differs from the canonical structures in that the first beta-strand is shorter and is nearer to the second beta-strand rather than to the third beta-strand on the C-terminus. There is also a large hydrophobic patch on the surface of the toxin, surrounding a central lysine residue, Lys13. We postulate that this hydrophobic patch is likely to form part of the binding surface of the toxin. (C) 2003 Published by Elsevier Science B.V. on behalf of the Federation of European Biochemical Societies.

Cytotoxic iron chelators: Characterization of the structure, solution chemistry and redox activity of ligands and iron complexes of the di-2-pyridyl ketone isonicotinoyl hydrazone (HPKIH) analogues

Di-2-pyridyl ketone isonicotinoyl hydrazone (HPKIH) and a range of its analogues comprise a series of monobasic acids that are capable of binding iron (Fe) as tridentate (N,N,O) ligands. Recently, we have shown that these chelators are highly cytotoxic, but show selective activity against cancer cells. Particularly interesting was the fact that cytotoxicity of the HPKIH analogues is maintained even after complexation with Fe. To understand the potent anti-tumor activity of these compounds, we have fully characterized their chemical properties. This included examination of the solution chemistry and X-ray crystal structures of both the ligands and Fe complexes from this class and the ability of these complexes to mediate redox reactions. Potentiometric titrations demonstrated that all chelators are present predominantly in their charge-neutral form at physiological pH (7.4), allowing access across biological membranes. Keto-enol tautomerism of the ligands was identified, with the tautomers exhibiting distinctly different protonation constants. Interestingly, the chelators form low-spin (diamagnetic) divalent Fe complexes in solution. The chelators form distorted octahedral complexes with Fe-II, with two tridentate ligands arranged in a meridional fashion. Electrochemistry of the Fe complexes in both aqueous and non-aqueous solutions revealed that the complexes are oxidized to their ferric form at relatively high potentials, but this oxidation is coupled to a rapid reaction with water to form a hydrated (carbinolamine) derivative, leading to irreversible electrochemistry. The Fe complexes of the HPKIH analogues caused marked DNA degradation in the presence of hydrogen peroxide. This observation confirms that Fe complexes from the HPKIH series mediate Fenton chemistry and do not repel DNA. Collectively, studies on the solution chemistry and structure of these HPKIH analogues indicate that they can bind cellular Fe and enhance its redox activity, resulting in oxidative damage to vital biomolecules.

Effect of pore-network connectivity on multicomponent adsorption of large molecules

The effect of pore-network connectivity on binary liquid-phase adsorption equilibria using the ideal adsorbed solution theory (LAST) was studied. The liquid-phase binary adsorption experiments used ethyl propionate, ethyl butyrate, and ethyl isovalerate as the adsorbates and commercial activated carbons Filtrasorb-400 and Norit ROW 0.8 as adsorbents. As the single-component isotherm, a modified Dubinin-Radushkevich equation was used. A comparison with experimental data shows that incorporating the connectivity of the pore network and considering percolation processes associated with different molecular sizes of the adsorptives in the mixture, as well as their different corresponding accessibility, can improve the prediction of binary adsorption equilibria using the LAST Selectivity of adsorption for the larger molecule in binary systems increases with an increase in the pore-network coordination number, as well with an increase in the mean pore width and in the spread of the pore-size distribution.

A creative solution for rapid and inexpensive model-making in product design processes

Innovative Developments in Virtual and Physical Prototyping

Growth and nutrient uptake of coffee seedlings cultivated in nutrient solution with and without silicon addition

In recent years, the application of silicon (Si) in crops, including coffee, has become a common practice. The objective of this study was to assess the silicon uptake by coffee seedlings and its effects on plant growth, water and macro and micronutrient uptake. The research was conducted using nutrient solution in a greenhouse at the Departamento de Fitotecnia da Universidade Federal de Viçosa, in a completely randomized design with two treatments (with and without silicon) and three replications. Each plot consisted of three plants grown in a 800 mL vessel containing the treatment solutions. At every three days, water consumption, the concentration of OH - and the depletion of Si and K were assessed in the nutrient solutions. After 33 days, the plants were assessed with regard to their fresh and dry weight of leaves, roots and stem, shoot height and total length of the plant (shoot and root). Number of leaves and internodes, and the content and accumulation of silicon, macro, and micronutrients were also determined. The consumption of water, the amount of potassium uptake and, biomass accumulation were greater in plants grown in solution without silicon addition. However, the concentration of OH- in the solution and the amount of silicon uptake were greater in plants grown in solution with added silicon. Silicon accumulation was greater in leaves than in stem and roots. Silicon decreased coffee plant accumulation of phosphorus, potassium, calcium, zinc, copper and iron.

Effect of N and K doses in nutritive solution on growth, production and coffee bean size

An adequate supply of nutrients is essential for obtaining high yields of coffee. The objective of this study was to evaluate the effect of N, K and the N:K ratio on vegetative and reproductive growth of coffee. For this purpose, coffee plants were grown in nutrient solution containing K in the concentrations of 1.08; 2.15; 3.23 and 5.38 mmol L-1 combined with a dose of 6 mmol L-1 N, resulting in the N:K ratios (w/w): 1:0.5; 1:1; 1:1.5 and 1:2.5. The control treatment consisted of the doses 3 and 1.61 mmol L-1 of N and K respectively, resulting in the N:K ratio (w/w) 1.0:1.5. The following variables were evaluated: height, stem diameter, number of nodes of the eighth plagiotrofic branch (index branch), pairs of plagiotrofic branches and number of nodes in the orthotropic branch every three weeks from the beginning of the experiment. Additionally, it was evaluated the chemical composition of processed beans and leaves between the flowering and the rapid expansion stage of the cherry beans, production of cherry beans per plant and classification of beans according to the size. N influenced mainly the characteristics of vegetative growth and K influenced mainly the reproductive growth evaluated by the production. The lowest production resulted in the highest percentages of beans retained on sieves with holes larger than 16/64", while the highest production promoted an increase in the percentage of beans retained on sieves with holes smaller than 16/64".

A creative solution for rapid and inexpensive model-making in product design processes

Rapid prototyping (RP) is an approach for automatically building a physical object through solid freeform fabrication. Nowadays, RP has become a vital aspect of most product development processes, due to the significant competitive advantages it offers compared to traditional manual model making. Even in academic environments, it is important to be able to quickly create accurate physical representations of concept solutions. Some of these can be used for simple visual validation, while others can be employed for ergonomic assessment by potential users or even for physical testing. However, the cost of traditional RP methods prevents their use in most academic environments on a regular basis, and even for very preliminary prototypes in many small companies. That results in delaying the first physical prototypes to later stages, or creating very rough mock-ups which are not as useful as they could be. In this paper we propose an approach for rapid and inexpensive model-making, which was developed in an academic context, and which can be employed for a variety of objects.

Hydraulic conductivity in response to exchangeable sodium percentage and solution salt concentration

Hydraulic conductivity is determined in laboratory assays to estimate the flow of water in saturated soils. However, the results of this analysis, when using distilled or deionized water, may not correspond to field conditions in soils with high concentrations of soluble salts. This study therefore set out to determine the hydraulic conductivity in laboratory conditions using solutions of different electrical conductivities in six soils representative of the State of Pernambuco, with the exchangeable sodium percentage adjusted in the range of 5-30%. The results showed an increase in hydraulic conductivity with both decreasing exchangeable sodium percentage and increasing electrical conductivity in the solution. The response to the treatments was more pronounced in soils with higher proportion of more active clays. Determination of hydraulic conductivity in laboratory is routinely performed with deionized or distilled water. However, in salt affected soils, these determinations should be carried out using solutions of electrical conductivity different from 0 dS m-1, with values close to those determined in the saturation extracts.

Une énigme lacanienne et sa solution ou comment «bâtir en France une nouvelle Athènes»

A data da emergência do «Discurso da Universidade» em Lacan introduz uma pontuação cronológica que parece carecer de plausibilidade, já que cerca de 350 anos separam o que se ensina na antiga Atenas da construção medieval da Universidade. Este artigo explica o que leva Lacan a dar as suas datas.

Self-interacting scalar field cosmologies: unified exact solutions and symmetries

We investigate a mechanism that generates exact solutions of scalar field cosmologies in a unified way. The procedure investigated here permits to recover almost all known solutions, and allows one to derive new solutions as well. In particular, we derive and discuss one novel solution defined in terms of the Lambert function. The solutions are organised in a classification which depends on the choice of a generating function which we have denoted by x(phi) that reflects the underlying thermodynamics of the model. We also analyse and discuss the existence of form-invariance dualities between solutions. A general way of defining the latter in an appropriate fashion for scalar fields is put forward.

Field effect and light-assisted a-Si:H sensors for detection of ions in solution

In this paper we present an amorphous silicon device that can be used in two operation modes to measure the concentration of ions in solution. While crystalline devices present a higher sensitivity, their amorphous counterpart present a much lower fabrication cost, thus enabling the production of cheap disposable sensors for use, for example, in the food industry. The devices were fabricated on glass substrates by the PECVD technique in the top gate configuration, where the metallic gate is replaced by an electrolytic solution with an immersed Ag/AgCl reference electrode. Silicon nitride is used as gate dielectric enhancing the sensitivity and passivation layer used to avoid leakage and electrochemical reactions. In this article we report on the semiconductor unit, showing that the device can be operated in a light-assisted mode, where changes in the pH produce changes on the measured ac photocurrent. In alternative the device can be operated as a conventional ion selective field effect device where changes in the pH induce changes in the transistor's threshold voltage.

Equilibrium self-assembly of colloids with distinct interaction sites: Thermodynamics, percolation, and cluster distribution functions

We calculate the equilibrium thermodynamic properties, percolation threshold, and cluster distribution functions for a model of associating colloids, which consists of hard spherical particles having on their surfaces three short-ranged attractive sites (sticky spots) of two different types, A and B. The thermodynamic properties are calculated using Wertheim's perturbation theory of associating fluids. This also allows us to find the onset of self-assembly, which can be quantified by the maxima of the specific heat at constant volume. The percolation threshold is derived, under the no-loop assumption, for the correlated bond model: In all cases it is two percolated phases that become identical at a critical point, when one exists. Finally, the cluster size distributions are calculated by mapping the model onto an effective model, characterized by a-state-dependent-functionality (f) over bar and unique bonding probability (p) over bar. The mapping is based on the asymptotic limit of the cluster distributions functions of the generic model and the effective parameters are defined through the requirement that the equilibrium cluster distributions of the true and effective models have the same number-averaged and weight-averaged sizes at all densities and temperatures. We also study the model numerically in the case where BB interactions are missing. In this limit, AB bonds either provide branching between A-chains (Y-junctions) if epsilon(AB)/epsilon(AA) is small, or drive the formation of a hyperbranched polymer if epsilon(AB)/epsilon(AA) is large. We find that the theoretical predictions describe quite accurately the numerical data, especially in the region where Y-junctions are present. There is fairly good agreement between theoretical and numerical results both for the thermodynamic (number of bonds and phase coexistence) and the connectivity properties of the model (cluster size distributions and percolation locus).

Simple thermodynamics of jet engines

We use the first and second laws of thermodynamics to analyze the behavior of an ideal jet engine. Simple analytical expressions for the thermal efficiency, the overall efficiency, and the reduced thrust are derived. We show that the thermal efficiency depends only on the compression ratio r and on the velocity of the aircraft. The other two performance measures depend also on the ratio of the temperature at the turbine to the inlet temperature in the engine, T-3/T-i. An analysis of these expressions shows that it is not possible to choose an optimal set of values of r and T-3/T-i that maximize both the overall efficiency and thrust. We study how irreversibilities in the compressor and the turbine decrease the overall efficiency of jet engines and show that this effect is more pronounced for smaller T-3/T-i.

Percolation of colloids with distinct interaction sites

We generalize the Flory-Stockmayer theory of percolation to a model of associating (patchy) colloids, which consists of hard spherical particles, having on their surfaces f short-ranged-attractive sites of m different types. These sites can form bonds between particles and thus promote self-assembly. It is shown that the percolation threshold is given in terms of the eigenvalues of a m x m matrix, which describes the recursive relations for the number of bonded particles on the ith level of a cluster with no loops; percolation occurs when the largest of these eigenvalues equals unity. Expressions for the probability that a particle is not bonded to the giant cluster, for the average cluster size and the average size of a cluster to which a randomly chosen particle belongs, are also derived. Explicit results for these quantities are computed for the case f = 3 and m = 2. We show how these structural properties are related to the thermodynamics of the associating system by regarding bond formation as a (equilibrium) chemical reaction. This solution of the percolation problem, combined with Wertheim's thermodynamic first-order perturbation theory, allows the investigation of the interplay between phase behavior and cluster formation for general models of patchy colloids.

Enthalpies of Solution of 1-Butyl-3-methylimidazolium Tetrafluoroborate in 15 Solvents at 298.15 K

Enthalpies of solution of 1-butyl-3-methylimidazolium tetra fluoroborate, [BMIm]BF4, are reported at 298.15 K in a set of 15 hydrogen bond donor and hydrogen bond acceptor solvents, chosen by their diversity, namely, water, methanol, ethanol, 1,2-ethanediol, 2-choroethanol, 2-methoxyethanol, formamide, propylene carbonate, nitromethane, acetonitrile, dimethyl sulfoxide, acetone, N,N-dimethylformamide, N,N-dimethylacetamide, and aniline. These values are shown to be largely independent of [BMIm]BF4 concentration. The obtained enthalpies of solution vary from very endothermic to quite exothermic, thus showing a very high sensitivity of the enthalpies of solution of [BMIm]BF4 to solvent properties. Solvent effects on the solution process of this IL are analyzed by a quantitative structure-property relationship methodology, using the TAKA equation and a modified equation, which significantly improves the model's predictive ability. The observed differences in the enthalpies of solution are rationalized in terms of the solvent properties found to be relevant, that is, pi* and E-T(N).