AVALIAÇÃO DO RADICAL N,N-DIETIL-1,4-FENILENODIAMINO (DEPD•+) COMO SONDA ESPECTROFOTOMÉTRICA PARA DETERMINAÇÃO DA CAPACIDADE ANTIOXIDANTE EM BEBIDAS

AbstractMany well-established methods for determining the antioxidant capacities in several samples have been described in literature. However, DPPH (2,2-diphenyl-1-picrylhydrazyl) and ABTS (2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid)) are the main two methods that utilize radicals as spectrophotometric probes for analysis. Nevertheless, these methods have certain limitations because of their slower kinetics, solvent polarity effects, the hydrophilicity and lipophilicity of the compounds, chemical costs, etc. In this study, a spectrophotometric method for determining the antioxidant capacity in beverages was developed based on an exploration of the cation radical derived from DEPD. This method was based on the oxidation of aromatic amines with Fe(III) ions at pH 4.0, which leads to their corresponding purple cation radicals (DEPD•+) with λmax values at 500 and 540 nm. The addition of an antioxidant after the formation of the radical leads to a reduction in color intensity that is proportional to the antioxidant concentration in the medium. Results obtained using this method were compared with the Folin-Ciocalteau, ABTS and DPPH methods in terms of applications in wines, teas, and infusions samples. Linear correlation analysis at a 95% confidence level was employed to compare the results, which were in good agreement with a correlation coefficient of r > 0.9000. Thus, the developed method was simple, accurate, and consistent with other assays for the determination of the total amount of phenolic compounds and antioxidant capacity.

Variability of the coat protein gene of Grapevine leafroll-associated virus 3 in Brazil

Leafroll is an economically important disease affecting grapevines (Vitis spp.). Nine serologically distinct viruses, Grapevine leafroll-associated virus-1 through 9, are associated with this disease. The present study describes the coat protein gene sequence of four GLRaV-3 isolates occurring in the São Francisco River basin, Northeastern Brazil. The viral RNA was extracted from GLRaV-3 ELISA-positive plants and the complete coat protein gene was amplified by RT-PCR. Sequences were generated automatically and compared to the complete coat protein sequence from North American (NY1) and Chinese (Dawanhong Nº2 and SL10) GLRaV-3 isolates. The four studied isolates, named Pet-1 through 4, showed deduced amino acid identities of 98-100% (Pet-1 through 3) and 95% (Pet-4) with North American and Chinese isolates. A total of seventeen amino acid substitutions was detected among the four characterized isolates in comparison to the NY1, Dawanhong No.2 and SL10 sequences. The results indicated the existence of natural variation among GLRaV-3 isolates from grapevines, also demonstrating a lack of correlation between sequence data and geographic origin. This variability should be considered when selecting regions of the viral genome targeted for reliable and consistent virus molecular detection.

Spatial and Spectral Separability of Grasslands in the inner Turku Archipelago using Landsat Thematic Mapper Satellite Imagery

The present study investigates the spatial and spectral discrimination potential for grassland patches in the inner Turku Archipelago using Landsat Thematic Mapper satellite imagery. The spatial discrimination potential was computed through overlay analysis using official grassland parcel data and a hypothetical 30 m resolution satellite image capturing the site. It found that Landsat TM imagery’s ability to retrieve pure or near-pure pixels (90% purity or more) from grassland patches smaller than 1 hectare was limited to 13% success, compared to 52% success when upscaling the resolution to 10 x 10 m pixel size. Additionally, the perimeter/area patch metric is proposed as a predictor for the suitability of the spatial resolution of input imagery. Regression analysis showed that there is a strong negative correlation between a patch’s perimeter/area ratio and its pure pixel potential. The study goes on to characterise the spectral response and discrimination potential for the five main grassland types occurring in the study area: recreational grassland, traditional pasture, modern pasture, fodder production grassland and overgrown grassland. This was done through the construction of spectral response curves, a coincident spectral plot and a contingency matrix as well as by calculating the transformed divergence for the spectral signatures, all based on training samples from the TM imagery. Substantial differences in spectral discrimination potential between imagery from the beginning of the growing season and the middle of summer were found. This is because the spectral responses for these five grassland types converge as the peak of the growing season draws nearer. Recreational grassland shows a consistent discrimination advantage over other grassland types, whereas modern pasture is most easily confused. Traditional pasture land, perhaps the most biologically valuable grassland type, can be spectrally discriminated from other grassland types with satisfactory success rates provided early growing season imagery is used.

Evaluation of group electronegativities and hardness (softness) of group 14 elements and containing functional groups through density functional theory and correlation with NMR spectra data

Quantum Chemical calculations for group 14 elements of Periodic Table (C, Si, Ge, Sn, Pb) and their functional groups have been carried out using Density Functional Theory (DFT) based reactivity descriptors such as group electronegativities, hardness and softness. DFT calculations were performed for a large series of tetracoordinated Sn compounds of the CH3SnRR'X type, where X is a halogen and R and R' are alkyl, halogenated alkyl, alkoxy, or alkyl thio groups. The results were interpreted in terms of calculated electronegativity and hardness of the SnRR'X groups, applying a methodology previously developed by Geerlings and coworkers (J. Phys. Chem. 1993, 97, 1826). These calculations allowed to see the regularities concerning the influence of the nature of organic groups RR' and inorganic group X on electronegativities and hardness of the SnRR'X groups; in this case, it was found a very good correlation between the electronegativity of the fragment and experimental 119Sn chemical shifts, a property that sensitively reflects the change in the valence electronic structure of molecules. This work was complemented with the study of some compounds of the EX and ER types, where E= C, Si, Ge, Sn and R= CH3, H, which was performed to study the influence that the central atom has on the electronegativity and hardness of molecules, or whether these properties are mainly affected for the type of ligand bound to the central atom. All these calculations were performed using the B3PW91 functional together with the 6-311++G** basis set level for H, C, Si, Ge, F, Cl and Br atoms and the 3-21G for Sn and I atoms.

Tilinpäätösinformaation läpinäkyvyyden muutokset pohjoismaissa IFRS-standardeihin siirtymisen jälkeen

EU:n alueella julkisesti listatut yritykset siirtyivät käyttämään konsernitilinpäätöksissään IFRS standardeja vuodesta 2005 alkaen. Yhtenä syynä standardien käyttöönotolle oli lisääntynyt tarve tilinpäätösinformaation läpinäkyvyydelle. Tässä tutkimuksessa tutkitaan, onko listattujen pohjoismaisten yritysten tilinpäätösinformaation läpinäkyvyys parantunut IFRS standardeihin siirtymisen jälkeen. Tilinpäätösinformaation läpinäkyvyys koostuu oikea-aikaisuudesta ja tuloslaskelmapohjaisesta konservatiivisuudesta, jotka analysoidaan kvantitatiivisesti. Tilinpäätösinformaation läpinäkyvyys on parantunut, jos oikea-aikaisuus on kasvanut ja tuloslaskelmapohjainen konservatiivisuus madaltunut. Näin ei kuitenkaan ole käynyt analysoitavien ensimmäisten neljän vuoden aikana, eikä tasepohjaisen konservatiivisuuden todeta vaikuttaneen tuloksiin konservatiivisuuksien mittareiden negatiivisen korrelaation kautta. Tuloksiin voi vaikuttaa standardien käyttöönoton alkuvaikeudet sekä euroaluetta ja Yhdysvaltoja kohdannut rahoituskriisi tarkastelujakson loppu puolella.

The role of van der Waals interactions in the case of H2 adsorption on ruthenium (0001) surface

Computational material science with the Density Functional Theory (DFT) has recently gained a method for describing, for the first time the non local bonding i.e., van der Waals (vdW) bonding. The newly proposed van der Waals-Density Functional (vdW-DF) is employed here to address the role of non local interactions in the case of H2 adsorption on Ru(0001) surface. The later vdW-DF2 implementation with the DFT code VASP (Vienna Ab-initio Simulation Package) is used in this study. The motivation for studying H2 adsorption on ruthenium surface arose from the interest to hydrogenation processes. Potential energy surface (PES) plots are created for adsorption sites top, bridge, fcc and hcp, employing the vdW-DF2 functional. The vdW-DF yields 0.1 eV - 0.2 eV higher barriers for the dissociation of the H2 molecule; the vdW-DF seems to bind the H2 molecule more tightly together. Furthermore, at the top site, which is found to be the most reactive, the vdW functional suggests no entrance barrier or in any case smaller than 0.05 eV, whereas the corresponding calculation without the vdW-DF does. Ruthenium and H2 are found to have the opposite behaviors with the vdW-DF; Ru lattice constants are overestimated while H2 bond length is shorter. Also evaluation of the CPU time demand of the vdW-DF2 is done from the PES data. From top to fcc sites the vdW-DF computational time demand is larger by 4.77 % to 20.09 %, while at the hcp site it is slightly smaller. Also the behavior of a few exchange correlation functionals is investigated along addressing the role of vdW-DF. Behavior of the different functionals is not consistent between the Ru lattice constants and H2 bond lengths. It is thus difficult to determine the quality of a particular exchange correlation functional by comparing equilibrium separations of the different elements. By comparing PESs it would be computationally highly consuming.

Correlation between the Alvarado Scale and the macroscopic aspect of the appendix in patients with appendicitis

Objective: To evaluate the possible association between the scale of Alvarado (EA) and macroscopic appearance (MA) of the appendix in patients with acute appendicitis.Methods: after receiving the diagnosis of acute appendicitis, EA data were collected. During appendectomy, MA data were collected. Data from patients without appendicitis were excluded. The Spearman correlation test was used to compare EA with Appendix MA (p < 0.05). Other variables were represented by simple frequency. The confidence interval (CI) of 95% was calculated for the correlation test.Results: Data were collected from 67 consecutive patients. The mean age was 37.1 ± 12.5 years and 77.6% of patients were male. The Spearman correlation test used for EA and MA was + 0.77 (95% CI 0.65-0.85, p < 0.0001).Conclusion: although correlation was not perfect, our data indicate that a high score on the scale of Alvarado in patients with appendicitis is correlated with advanced stages of the inflammatory process of acute appendicitis.

Correlation between the oropharyngo-laryngoscopic findings and the severity of obstructive sleep apnea

Objective: To correlate anatomical and functional changes of the oral cavity, pharynx and larynx to the severity of obstructive sleep apnea syndrome (OSAS). Methods : We conducted a cross-sectional study of 66 patients of both genders, aged between 21 and 59 years old with complaints of snoring and / or apnea. All underwent full clinical evaluation, including physical examination, nasolarybgoscopy and polisonography. We classified individuals into groups by the value of the apnea-hypopnea index (AHI), calculated measures of association and analyzed differences by the Kruskal-Wallis and chi-square tests. Results : all patients with obesity type 2 had OSAS. We found a relationship between the uvula projection during nasoendoscopy and OSAS (OR: 4.9; p-value: 0.008; CI: 1.25-22.9). In addition, there was a major strength of association between the circular shape of the pharynx and the presence of moderate or severe OSAS (OR: 9.4, p-value: 0.002), although the CI was wide (1.80-53.13). The septal deviation and lower turbinate hypertrophy were the most frequent nasal alterations, however unrelated to gravity. Nasal obstruction was four times more common in patients without daytime sleepiness. The other craniofacial anatomical changes were not predictors for the occurrence of OSAS. Conclusion : oral, pharyngeal and laryngeal disorders participate in the pathophysiology of OSAS. The completion of the endoscopic examination is of great value to the evaluation of these patients.

Correlation between placental thickness in the second and third trimester and fetal weight

PURPOSE: To investigate relationship between placental thickness during the second and third trimesters and placental and birth weights. METHODS: From January 2011 to June 2012, a total of 250 singleton pregnant women presented at our antenatal clinic were enrolled in this prospective study. All recruited women were assessed at the 1st trimester screening for baseline demographic and obstetric data. The placental thickness was measured trans-abdominally by placing the ultrasound transducer perpendicularly to the plane of the placenta, in the area of the cord insertion at second and third trimester. Pearson's correlation analysis was used to establish the degree of relationship between placental thickness and birth and placental weights. RESULTS: Of 250 recruited participants, 205 women were able to complete the study. The mean age of cases was 26.4±5.1. Values of mean birth and placental weights were 305.56±657.0 and 551.7±104.8 grams respectively. Ultrasonographic measures of placental thickness in second and third trimester and changes between them were 21.68±4.52, 36.26±6.46 and 14.67±5.67 mm respectively. There was a significant positive correlation between placental thickness and birth weight in the second and third trimesters (r=0.15, p=0.03; r=0.14, p=0.04 correspondingly). CONCLUSION: According to our study, birth weight has a positive relation with both second and third trimester placental thickness; however, placental thickness change could not predict low birth weight.

Immunohistochemical evaluation of e-cadherin, Ki-67 and PCNA in canine mammary neoplasias: correlation of prognostic factors and clinical outcome

E-cadherin is a cell-cell adhesion molecule and low e-cadherin expression is related to invasiveness and may indicate a bad prognosis in mammary neoplasms. The expression of cell proliferation markers PCNA and especially Ki-67, has also proved to have a strong prognostic value in this tumor class. The expression of these markers was related to the clinical-pathological characteristics of 73 surgically removed mammary tumors in female dogs by immunohistochemistry. There was no statistical correlation between these markers and death by neoplasm, survival time and disease-free interval. However, the loss of e-cadherin expression and marked Ki-67 expression (p=0.016) were considered statistically significant for the diagnosis (p=0.032). When evaluated as independent factors, there was evidence of the relationship between the loss of e-cadherin expression and high PCNA expression with changes in the body status (divided into obese, normal and cachectic) of female dogs (p=0.030); there was also evidence of the relationship between pseudopregnancy and e-cadherin alone (p=0.021) and for ulceration and PCNA alone (p=0.035). The significant correlation between the markers expression and these well known prognostic factors used individually or in combination suggests their prognostic value in canine mammary tumors.

Experimental poisoning of goats by Ipomoea carnea subsp. fistulosa in Argentina: a clinic and pathological correlation with special consideration on the central nervous system

Ipomoea carnea subsp. fistulosa, aguapei or mandiyura, is responsible for lysosomal storage in goats. The shrub contains several alkaloids, mainly swansonine which inhibits lysosomal α-mannosidase and Golgi mannosidase II. Poisoning occurs by inhibition of these hydrolases. There is neuronal vacuolation, endocrine dysfunction, cardiovascular and gastrointestinal injury, and immune disorders. Clinical signs and pathology of the experimental poisoning of goats by Ipomoea carnea in Argentina are here described. Five goats received fresh leaves and stems of Ipomoea. At the beginning, the goats did not consume the plant, but later, it was preferred over any other forage. High dose induced rapid intoxication, whereas with low doses, the course of the toxicosis was more protracted. The goats were euthanized when they were recumbent. Cerebrum, cerebellum, medulla oblongata, pons and colliculi, were routinely processed for histology. In nine days, the following clinical signs developed: abnormal fascies, dilated nostrils and abnormal postures of the head, cephalic tremors and nystagmus, difficulty in standing. Subsequently, the goats had a tendency to fall, always to the left, with spastic convulsions. There was lack in coordination of voluntary movements due to Purkinje and deep nuclei neurons damage. The cochlear reflex originated hyperreflexia, abnormal posture, head movements and tremors. The withdrawal reflex produced flexor muscles hypersensitivity at the four legs, later depression and stupor. Abnormal responses to sounds were related to collicular lesions. Thalamic damage altered the withdrawal reflex, showing incomplete reaction. The observed cervical hair bristling was attributed to a thalamic regulated nociceptive response. Depression may be associated with agonists of lysergic acid contained in Ipomoea. These clinical signs were correlated with lesions in different parts of the CNS.

Contact with friction using the augmented Lagrangian Method: a conditional constrained minimization problem

This work presents a formulation of the contact with friction between elastic bodies. This is a non linear problem due to unilateral constraints (inter-penetration of bodies) and friction. The solution of this problem can be found using optimization concepts, modelling the problem as a constrained minimization problem. The Finite Element Method is used to construct approximation spaces. The minimization problem has the total potential energy of the elastic bodies as the objective function, the non-inter-penetration conditions are represented by inequality constraints, and equality constraints are used to deal with the friction. Due to the presence of two friction conditions (stick and slip), specific equality constraints are present or not according to the current condition. Since the Coulomb friction condition depends on the normal and tangential contact stresses related to the constraints of the problem, it is devised a conditional dependent constrained minimization problem. An Augmented Lagrangian Method for constrained minimization is employed to solve this problem. This method, when applied to a contact problem, presents Lagrange Multipliers which have the physical meaning of contact forces. This fact allows to check the friction condition at each iteration. These concepts make possible to devise a computational scheme which lead to good numerical results.

Is there correlation between the turbulent eddies size and mechanical hemolysis ?

Hemolytic profile of an artificial device chronically implanted in the cardiovascular system may represent the difference between the success and failure in its long-term performance. Last decades have witnessed efforts on the development of methods capable of predicting red blood cell damage in artificial organs. However, all of them have had limited success to predict hemolysis. The primary cause of this problem is that such models do not take into consideration structures of turbulent flow. The present paper demonstrates that microscopic measurable occurrences of the turbulent flow may be linked to red blood cell trauma. This study suggests that if the smallest turbulent eddies dimension is under 10 m m hemolysis is not dependent on the exposure time and the red blood cells damage depends only on the dissipation of the turbulent energy in the erythrocyte membrane. The analysis reported here opens the possibility of mapping the flow field in artificial assist devices based on the smallest eddy length scales. This is a promising new trend and should be considered in the designing requirements of the next generations of artificial organs.

Risk-return trade-off and autocorrelation

A trade-off between return and risk plays a central role in financial economics. The intertemporal capital asset pricing model (ICAPM) proposed by Merton (1973) provides a neoclassical theory for expected returns on risky assets. The model assumes that risk-averse investors (seeking to maximize their expected utility of lifetime consumption) demand compensation for bearing systematic market risk and the risk of unfavorable shifts in the investment opportunity set. Although the ICAPM postulates a positive relation between the conditional expected market return and its conditional variance, the empirical evidence on the sign of the risk-return trade-off is conflicting. In contrast, autocorrelation in stock returns is one of the most consistent and robust findings in empirical finance. While autocorrelation is often interpreted as a violation of market efficiency, it can also reflect factors such as market microstructure or time-varying risk premia. This doctoral thesis investigates a relation between the mixed risk-return trade-off results and autocorrelation in stock returns. The results suggest that, in the case of the US stock market, the relative contribution of the risk-return trade-off and autocorrelation in explaining the aggregate return fluctuates with volatility. This effect is then shown to be even more pronounced in the case of emerging stock markets. During high-volatility periods, expected returns can be described using rational (intertemporal) investors acting to maximize their expected utility. During lowvolatility periods, market-wide persistence in returns increases, leading to a failure of traditional equilibrium-model descriptions for expected returns. Consistent with this finding, traditional models yield conflicting evidence concerning the sign of the risk-return trade-off. The changing relevance of the risk-return trade-off and autocorrelation can be explained by heterogeneous agents or, more generally, by the inadequacy of the neoclassical view on asset pricing with unboundedly rational investors and perfect market efficiency. In the latter case, the empirical results imply that the neoclassical view is valid only under certain market conditions. This offers an economic explanation as to why it has been so difficult to detect a positive tradeoff between the conditional mean and variance of the aggregate stock return. The results highlight the importance, especially in the case of emerging stock markets, of noting both the risk-return trade-off and autocorrelation in applications that require estimates for expected returns.

Correlation of soil properties with weed ocurrence in sugarcane areas

Soil properties can influence weed community composition and weed density agricultural area. Knowing this relationship would allow to choose the best strategy for the control of such plants. This study aimed to investigate the correlation between weed density and chemical and physical attributes of soil in three areas (UCO, USC, and UPA) for commercial sugarcane cultivation in Campos dos Goytacazes, RJ. Grids of 40 m x 40 m were established in the areas, and soil samples were collected at the intersection points for physical and chemical analysis and evaluation of the soil seed bank (SSB), followed by a phyto-sociological survey of the weeds present. Samples were collected during two periods: February/March and June/July, 2010. SSB presented the greatest number of species per vegetation evaluated in the two sampling periods. Clay content had a positive effect leading to greater weed density in all areas (UCO, USC and UPA) in at least one of the densities (0-10 and 10-20 cm). On the other hand, sand content, when significant, presented a negative correlation with plant density in all the SSB areas analyzed. The pH negatively influenced the density of the species found through the phyto-sociological survey at USC and UPA. Cyperus rotundus, dominant in all areas, correlated positively with phosphorus, potassium, and clay content and negatively with pH and high sand content.