Constraining the orbital orientation of eta Carinae from H Paschen lines

During the past decade, several observational and theoretical works have provided evidence of the binary nature of eta Carinae. Nevertheless, there is still no direct determination of the orbital parameters, and the different current models give contradictory results. The orbit is, in general, assumed to coincide with the Homunculus equator although the observations are not conclusive. Among all systems, eta Car has the advantage that it is possible to observe both the direct emission of line transitions in the central source and its reflection by the Homunculus, which is dependent on the orbital inclination. In this work, we studied the orbital phase-dependent hydrogen Paschen spectra reflected by the south-east lobe of the Homunculus to constrain the orbital parameters of eta Car and determine its inclination with respect to the Homunculus axis. Assuming that the emission excess originates in the wind-wind shock region, we were able to model the latitude dependence of the spectral line profiles. For the first time, we were able to estimate the orbital inclination of eta Car with respect to the observer and to the Homunculus axis. The best fit occurs for an orbital inclination to the line of sight of i similar to 60 degrees +/- 10 degrees, and i* similar to 35 degrees +/- 10 degrees with respect to the Homunculus axis, indicating that the angular momenta of the central object and the orbit are not aligned. We were also able to fix the phase angle of conjunction as similar to -40 degrees, showing that periastron passage occurs shortly after conjunction.

Seasonal metabolic changes in a year-round reproductively active subtropical tree-frog (Hypsiboas prasinus)

Although seasonal metabolic variation in ectothermic tetrapods has been investigated primarily in the context of species showing some level of metabolic depression during winter, but several species of anurans maintain their activity patterns throughout the year in tropical and subtropical areas. The tree-frog Hypsiboas prasinus occurs in the subtropical Atlantic Forest and remains reproductively active during winter, at temperatures below 10 degrees C. We compared males calling in summer and winter, and found that males of H. prasinus exhibit seasonal adjustments in metabolic and morphometric variables. Individuals calling during winter were larger and showed higher resting metabolic rates than those calling during summer. Calling rates were not affected by season. Winter animals showed lower liver and heart activity level of citrate synthase (CS), partially compensated by larger liver mass. Winter individuals also showed higher activity Of pyruvate kinase (PK) and lower activity of CS in trunk muscles, and higher activity of CS in leg muscles. Winter metabolic adjustments seem to be achieved by both compensatory mechanisms to the lower environmental temperature and a seasonally oriented aerobic depression of several organs. The impact of seasonal metabolic changes on calling performance and the capacity of subtropical anurans for metabolic thermal acclimatization are also discussed. (C) 2008 Elsevier Inc. All rights reserved.

Synthesis of biodegradable polyhydroxyalcanoate copolymer from a renewable source by alternate feeding

Polyhydroxyalcanoates copolymers with 3-hydroxybutirate (3HB) and 3-hydroxyvalerate (3HV) co-monomers, P3(HB-co-x%HV), were produced in fed-batch culture by Ralstonia eutropha DSM428 using fructose as a single carbon source in the first step and adding propionic acid in the second step by alternating feeding. Polymer yield was 0.18 g/L with a content of 24 mol% of the 3HV fraction determined by H-1 NMR. NMR measurements indicated that the polymer obtained is isotactic. The copolymer attained 35% of crystallinity according to X-ray diffraction measurements, and two (020) planes were observed. Thermal behavior presented melting temperature at 154 degrees C and the crystallization temperature was 65 degrees C. A glass transition temperature was observed at -10 degrees C. Average molecular weight measured by GPC was 4.9 x 10(5) Dalton. Isothermal radial growth rates of spherulites of P3(HB-co-24%HV) were studied. All experimental facts and the analysis of the sequence distribution of diads and triads of 3HB and 3HV units led to the conclusion that it is not a completely statistical random copolymer once it contains different types of segments. POLYM.

Melting Regime of the Anionic Phospholipid DMPG: New Lamellar Phase and Porous Bilayer Model

Aqueous dispersions of the anionic phospholipid dimyristoyl phosphatidylglycerol (DMPG) at pH above the apparent pK of DMPG and concentrations in the interval 70-300 mM have been investigated by small (SAXS) and wide-angle X-ray scattering, differential scanning calorimetry, and polarized optical microscopy. The order. disorder transition of the hydrocarbon chains occurs along an interval of about 10 degrees C (between T(m)(on) similar to 20 degrees C and T(m)(off) similar to 30 degrees C). Such melting regime was previously characterized at lower concentrations, up to 70 mM DMPG, when sample transparency was correlated with the presence of pores across the bilayer. At higher concentrations considered here, the melting regime persists but is not transparent. Defined SAXS peaks appear and a new lamellar phase L(p) with pores is proposed to exist above 70 mM DMPG, starting at similar to 23 degrees C (similar to 3 degrees C above T(m)(on)) and losing correlation after T(m)(off). A new model for describing the X-ray scattering of bilayers with pores, presented here, is able to explain the broad band attributed to in-plane correlation between pores. The majority of cell membranes have a net negative charge, and the opening of pores across the membrane tuned by ionic strength, temperature, and lipid composition is likely to have biological relevance.

Synthesis and structural characterization of a new polymeric zinc(II) complex with thiophene-2-carboxylic acid

A new polymeric zinc(II) complex with thiophene-2-carboxylic acid (-tpc) of composition [Zn2(C20H12O8S4)]n was obtained and structurally characterized by X-ray diffraction, thermal analysis, nuclear magnetic resonance (NMR), and infrared spectroscopies. Upfield shift in the 1H-NMR spectrum is explained by the crystalline structure, which shows the thiophene rings overlapping each other in parallel pairs. The compound crystallizes in the monoclinic system, space group P21/c, with a = 9.7074(4) angstrom, b = 13.5227(3) angstrom, c = 18.9735(7) angstrom, = 95.797(10)degrees, and Z = 4. Three -tpc groups bridge between two Zn(II) ions through oxygens and the fourth one bridges between one of these ions and the third one, symmetry related by a twofold screw axis. This arrangement gives rise to infinite chains along the crystallographic a direction. The metal atoms display an approximate tetrahedral configuration. The complex is insoluble in water, ethanol, and acetone, but soluble in dimethyl sulfoxide.

Temperature dependence of molecular dynamics and supramolecular aggregation in MEH-PPV films: A solid-state NMR, X-ray and fluorescence spectroscopy study

This article presents an investigation of the temperature induced modification in the microstructure and dynamics of poly[2-methoxy-5-(2`-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) cast films using Wide-Angle X-ray Scattering (WAXS), solid-state Nuclear Magnetic Resonance (NMR), and Fluorescence Spectroscopy (PL). MEH-PPV chain motions were characterized as a function of temperature by NMR. The results indicated that the solvent used to cast the films influences the activation energy of the side-chain motions. This was concluded from the comparison of the activation energy of the toluene cast film, E(a) = (54 +/- 8) kJ/mol, and chloroform cast film, E(a) = (69 +/- 5) kJ/mol, and could be attributed to the higher side-chain packing provided by chloroform, that preferentially solvates the side chain in contrast to toluene that solvates mainly the backbone. Concerning the backbone mobility, it was observed that the torsional motions in the MEH-PPV have average amplitude of similar to 10 degrees at 300 K, which was found to be independent of the solvent used to cast the films. In order to correlate the molecular dynamics processes with the changes in the microstructure of the polymer, in situ WAXS experiments as a function of temperature were performed and revealed that the interchain spacing in the MEH-PPV molecular aggregates increases as a function of temperature, particularly at temperatures where molecular relaxations occur. It was also observed that the WAXS peak associated with the bilayer spacing becomes narrower and its intensity increases whereas the peak associated with the inter-backbone planes reduces its intensity for higher temperatures. This last result Could be interpreted as a decrease in the number of aggregates and the reduction of the interchain species during the MEH-PPV relaxation processes. These WAXS results were correlated with PL spectra modifications observed upon temperature treatments. (C) 2008 Elsevier Ltd. All rights reserved.

Synthesis and structure of the dimeric copper(II) complex tetrakis[N-thiazol-2-yl-(4-methylphenyl)sulfonamidate]dicopper(II)

The coordination chemistry of the ligand N-thiazol-2-yl-toluenesulfonamidate towards the copper(II) ion has been investigated using an electrochemical synthesis method. The X-ray structure of this complex was elucidated and is discussed. The compound crystallised in the monoclinic crystal system, P2(1)/c space group with a = 17.3888(9), b = 16.3003(9), c = 18.3679(9) angstrom and beta = 114.3640(10)degrees. Four bidentate sulfathiazolato anions bridge two metal centers in a paddle-wheel fashion, with the nitrogen atoms as donors to give a dimeric species with a Cu center dot center dot center dot Cu distance of 2.7859(5) angstrom.

Crystal and molecular structures of three 2-sulphur-substituted cyclohexanones studied by X-ray crystallography and by ab initio molecular orbital calculations

The conformational features of three 2-sulphur-substituted cyclohexanone derivatives, which differ in the number of sulphur-bound oxygen atoms, i.e. zero (I), one (II) and two (III), were investigated by single crystal X-ray crystallography and geometry optimized structures determined using Hartree-Fock method. In each of (I)-(III) an intramolecular S center dot center dot center dot O(carbonyl) interaction is found with the magnitude correlated with the oxidation state of the sulphur atom, i.e. 2.838(3) angstrom in (I) to 2.924(2) angstrom in (II) to 3.0973(18) angstrom in (III). There is an inverse relationship between the strength of this interaction and the magnitude of the carbonyl bond. The supramolecular aggregation patterns are primarily determined by C-H center dot center dot center dot O contacts and are similarly influenced by the number of oxygen atoms in the molecular structures. Thus, a supramolecular chain is found in the crystal structure of (I). With an additional oxygen atom available to participate in C-H center dot center dot center dot O interactions, as in (II), a two-dimensional array is found. Finally, a three-dimensional network is found for (III). Despite there being differences in conformations between the experimental structures and those calculated in the gas-phase, the S center dot center dot center dot O interactions persist. The presence of intermolecular C-H center dot center dot center dot O interactions involving the cyclohexanone-carbonyl group in the solid-state, disrupts the stabilising intramolecular C-H center dot center dot center dot O interaction in the energetically-favoured conformation. (I): C(12)H(13)NO(3)S, triclinic space group P (1) over bar with a = 5.392(3) angstrom b = 10.731(6) angstrom, c = 11.075(6) angstrom, alpha = 113.424(4)degrees, beta = 94.167(9)degrees, gamma = 98.444(6)degrees, V = 575.5(6) angstrom(3), Z = 2, R(1) = 0.052; (II): C(12)H(13)NO(4)S, monoclinic P2(1)/n, a = 7.3506(15) angstrom, b = 6.7814(14) angstrom, c = 23.479(5) angstrom, beta = 92.94(3)degrees, V = 1168.8(4) angstrom(3), Z = 4, R(1) = 0.046; (III): C(12)H(13)NO(5)S, monoclinic P2(1)/c, a = 5.5491(11) angstrom, b = 24.146(3) angstrom, c = 11.124(3) angstrom, beta = 114.590(10)degrees, V = 1355.3(5) angstrom(3), Z = 4, R(1) = 0.051.

Temperature (over) compensation in an oscillatory surface reaction

Biological rhythms are regulated by homeostatic mechanisms that assure that physiological clocks function reliably independent of temperature changes in the environment. Temperature compensation, the independence of the oscillatory period on temperature, is known to play a central role in many biological rhythms, but it is rather rare in chemical oscillators. We study the influence of temperature on the oscillatory dynamics during the catalytic oxidation of formic acid on a polycrystalline platinum electrode. The experiments are performed at five temperatures from 5 to 25 degrees C, and the oscillations are studied under galvanostatic control. Under oscillatory conditions, only non-Arrhenius behavior is observed. Overcompensation with temperature coefficient (q(10), defined as the ratio between the rate constants at temperature T + 10 degrees C and at T) < I is found in most cases, except that temperature compensation with q(10) approximate to I predominates at high applied currents. The behavior of the period and the amplitude result from a complex interplay between temperature and applied current or, equivalently, the distance from thermodynamic equilibrium. High, positive apparent activation energies were obtained under voltammetric, nonoscillatory conditions, which implies that the non-Arrhenius behavior observed under oscillatory conditions results from the interplay among reaction steps rather than, from a weak temperature dependence of the individual steps.

Qualidade de abóbora minimamente processada armazenada em atmosfera modificada ativa

The active modified atmosphere effect was evaluated in the quality of squash fresh-cut (MP).. The squash pieces were conditioned in plastic packings and submitted the gases application in the following concentrations: 0.03% CO2 and 21% O-2 (controls T1); 5% CO2 and 4% O-2 (T2); 6% CO2 and 4% O-2 (T3); 7% CO2 and 4% O-2 (T4); 8% CO2 and 4% O-2 (T5). In T6 it was made vacuum application in the packing. The packings containing the squash were stored in to the temperature of 10 degrees C and relative humidity of 75% for 12 days. The evaluated analyses were weigth loss, total acidity (AT), pH, soluble solids (SS), ratio, firmness, color, antioxidant activity for DPPH and carotenoids content. The weigth loss was gradual and low until the ninth day of storage. The values of AT increased along the experimental period being superior for T1 and T2. The increase of SS during the storage of the fresh-cut squash went smaller for T3 and T4. The brightness stayed during the storage being superior for T5, already the color components red and yellow decreased along the experimental period.

Multivariate analysis of fresh-cut carambola slices stored under different temperatures

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

Use of modified atmosphere to extend shelf life of fresh-cut carambola (Averrhoa carambola L. cv. Fwang Tung)

Fresh-cut fruit products, including carambola (Averrhoa carambola L.), have limited marketability due to cut surface browning attributed to phenolic compound oxidation by enzymes, such as polyphenol oxidase (PPO). The objective of this study was to evaluate postharvest changes in carambola slices in three different packages. Carambola fruit (cv. Fwang Tung) were picked from the Estacao Experimental de Citricultura de Bebedouro orchard at the mature-green stage. The fruit were washed, dipped in NaOCl solution (200 mg L-1 for 5 min), stored overnight at 10 degrees C, then manually sliced into pieces of approximately 1 cm. The slices were rinsed with NaOCl solution at 20 mg L-1, drained for 3 min, and packaged in polyethylene terephthalate (PET) trays (Neoform (R) N94); polystyrene trays covered with PVC 0.017 turn (Vitafilm (R), Goodyear); and vacuum seated polyolefin bags (PLO, Cryovac (R) PD900). The packages were stored at 6.8 degrees C and 90% RH for 12 d, with samples taken every 4 d. PET trays and PVC film did not significantly modify the internal atmosphere and the high water permeability of PVC led to more rapid slice desiccation. PPO activity was lower when the slices were packaged in PLO vacuum sealed bags, which reduced degreening and led to better appearance maintenance for up to 12 d. (R) 2006 Elsevier B.V. All rights reserved.

Minimally processed guava fruits (Psidium guajava L.)

'Paluma' guavas, after internal quality evaluation using magnetic resonance tomography, were used to produce fresh-cut product. Fruits were peeled or not, cut in halves and seed removed, and they were packaged in polystyrene trays covered with PVC film or in a PET container with a lid. These packages were stored for 12 days at 5 degrees C, 10 degrees C and ambient temperature (22.6 degrees C). Tomography evaluation verified that impacts produced internal bruising with loss of cellular integrity and liquefication of the placenta tissues. Compression was more evident on the pericarp and cutting promoted superficial deformation. Storage temperature affected the weight loss, with fruit packaged in the polystyrene tray having a greater weight loss. The peeling did not influence weight loss. Product stored at 5 degrees C and 10 degrees C for 8 days had low microbial growth (< 10(3) UFC.g(-1)) and no coliforms. Rapid spoilage and a short shelf life (3-4 days) occurred when the product was stored at ambient temperature. Peeling reduced ascorbic acid concentration and total soluble solids. Use of calcium to protect fresh-cut products was not efficient. Calcium absorption capacity of 'Pedro Sato' guava was tested using Ca-45. Fruits treated with 2% CaCl2, with or without the radioisotope, were divided in four layers (epicarp, mesocarp, endocarp and seed) and analyzed for the total and Ca-45 calcium. It was observed that the applied calcium remained in superficial layers of fruits, which was confirmed by autoradiography. Internal layers did not contain Ca-45, indicating that calcium was not distributed into different parts of the fruit.

Postharvest Conservation of Mature-Green and Ripe 'Paluma' Guava Stored at Two Temperatures

This work aimed to establish the importance of maturation and ripeness stages and the use of refrigeration for the conservation of 'Paluma' guavas. Fruit picked at the mature-green and ripe stages were stored at ambient conditions (21 degrees C and 85% RH) and also at 10 degrees C (85% RH). The fruit were evaluated every 2 or 3 days for weight loss, appearance, decay, color, firmness, soluble solids, titratable acidity, ascorbic acid, total polyphenols extractable content and total antioxidant activity. The fruit stored at 21 degrees C had higher weight loss than those stored at 10 degrees C. Mature-green guavas at 21 degrees C remained in good quality for 6 days, but at 10 degrees C, the preservation period increased to 15 days. Ripe fruit were preserved for 4 days at 21 degrees C, which was extended with refrigeration to 6 days. Mature-green fruit at 21 degrees C had decay in 6 days; while at 10 degrees C decay happened in 18 days. The peel color of mature-green fruits, at 21 degrees C, showed increasing values of luminosity, indicating that its color became lighter (change from green to yellow) and at 10 degrees C it showed constant values until the end of storage. Pulp firmness of mature-green fruit declined during storage as a result of ripening. In ripe fruits such reduction occurred more slowly, since they were softer. The color of the pulp became intense red for mature fruits. Soluble solids were lower in ripe fruit at 21 degrees C, while in mature fruits at 10 degrees C, it increased. The titratable acidity increased in fruits stored at 10 degrees C. The fruits kept at 21 degrees C and the mature guavas kept at 10 degrees C showed no changes in ascorbic acid content. The ripe fruit at 10 degrees C maintained their ascorbic acid levels. Mature guavas, stored at 10 degrees C, had the longest shelf life and higher contents of soluble solids and titratable acidity, with no changes in total polyphenols extractable content and total antioxidant activity.

Adaptação eletrônica de um leitor mecânico de coto, investigação e desenvolvimento de interface CAD

Due to advances in the manufacturing process of orthopedic prostheses, the need for better quality shape reading techniques (i.e. with less uncertainty) of the residual limb of amputees became a challenge. To overcome these problems means to be able in obtaining accurate geometry information of the limb and, consequently, better manufacturing processes of both transfemural and transtibial prosthetic sockets. The key point for this task is to customize these readings trying to be as faithful as possible to the real profile of each patient. Within this context, firstly two prototype versions (α and β) of a 3D mechanical scanner for reading residual limbs shape based on reverse engineering techniques were designed. Prototype β is an improved version of prototype α, despite remaining working in analogical mode. Both prototypes are capable of producing a CAD representation of the limb via appropriated graphical sheets and were conceived to work purely by mechanical means. The first results were encouraging as they were able to achieve a great decrease concerning the degree of uncertainty of measurements when compared to traditional methods that are very inaccurate and outdated. For instance, it's not unusual to see these archaic methods in action by making use of ordinary home kind measure-tapes for exploring the limb's shape. Although prototype β improved the readings, it still required someone to input the plotted points (i.e. those marked in disk shape graphical sheets) to an academic CAD software called OrtoCAD. This task is performed by manual typing which is time consuming and carries very limited reliability. Furthermore, the number of coordinates obtained from the purely mechanical system is limited to sub-divisions of the graphical sheet (it records a point every 10 degrees with a resolution of one millimeter). These drawbacks were overcome by designing the second release of prototype β in which it was developed an electronic variation of the reading table components now capable of performing an automatic reading (i.e. no human intervention in digital mode). An interface software (i.e. drive) was built to facilitate data transfer. Much better results were obtained meaning less degree of uncertainty (it records a point every 2 degrees with a resolution of 1/10 mm). Additionally, it was proposed an algorithm to convert the CAD geometry, used by OrtoCAD, to an appropriate format and enabling the use of rapid prototyping equipment aiming future automation of the manufacturing process of prosthetic sockets.