Polymethine cyanine dyes in beta-cyclodextrin solution: multiple equilibria and chemical oxidation

Absorption and fluorescence spectroscopy, electrochemical techniques, and semiempirical calculations were employed to characterize the multiple complexation equilibria between two polymethine cyanine dyes (IR-786 and Indocyanine green-ICG, 5) and beta-cyclodextrin (beta-CD, L), as well as the chemical reactivity of the complexed and uncomplexed species against the oxidizing agents hypochlorite (HC) and hydrogen peroxide (HP). IR-786 dimerization is favored with the increase in beta-CD concentration in the form of (SL)(2) complexes. In the case of ICG, free dimers (D) and SL complexes are favored. Both IR-786 and ICG react and discolor in the presence of HC and HP. For IR-786, the reaction with HP and HC proceeds with observed rate constants of 10(-3) and 0.28 s(-1) and second-order rate constants (k(2)) of similar to 10(-3) and 10(4) M(-1) s(-1), respectively. The intermediate species observed in the bleaching reactions of IR-786 and ICG were shown, by cyclic voltammetry and VIS absorption, to result from one electron oxidation. IR-786 complexed with beta-CD is protected against bleaching in the presence of HP and HC by factors of 20 and 4, respectively. This protection was not observed in ICG complexes. Superdelocalizability profile of both dyes and frontier orbital analysis indicates that beta-CD does not protect ICG from oxidation by HP or HC, whereas the 2:2 IR-786/beta-Cd complex is able to avoid the oxidation of IR-786. We concluded that the decrease in the chemical reactivity of the dyes against oxidant agents in the presence of beta-CD is due to the formation of (SL)(2) complexes. Copyright (C) 2010 John Wiley & Sons, Ltd.

Removal of metal ions from aqueous solution by chelating polymeric hydrogel

Polysaccharide natural seed coat from the tree Magonia pubescens, in the form of hydrogel was used to remove metals in aqueous solution. Swelling tests indicate that seed coat presents hydrogel behavior, with maximum water absorption of 292 g water/g. Adsorption experiments performed using Na(+), Mg(2+), K(+), Ca(2+), Cr(3+), Fe(3+) and Zn(2+) demonstrated that the polysaccharide structure has a high capacity to extract these ions from the aqueous solution. Scanning electron microscopy revealed significant morphological changes of the material before and after water contact. Differential scanning calorimetry measurements indicate a signal shift of the water evaporation temperature in the material with adsorbed zinc. X-ray photoelectron spectroscopy analysis combined with theoretical studies by the density functional theory and on Hartree-Fock (HF) level evidence that the metallic ions were adsorbed through coordination with hydroxyl groups of polysaccharide. In the case of Zn(2+) the lowest HF energy was observed for the tetracoordination mode, where Zn(2+) is coordinated by two hydroxyl groups and two water molecules.

The role of oxygen in the interaction of emeraldine base polyaniline with Cu(II) or Fe(III) ions in NMP solution

The influence of molecular oxygen in the interactions of emeraldine base form of polyaniline (EB-PANI) with Fe(III) or Cu(II) ions in 1-methyl-2-pyrrolidinone (NMP) solutions has been investigated by UV-vis-NIR, resonance Raman and electron paramagnetic resonance (EPR) spectroscopies. Through the set of spectroscopic results it was possible to rationalize the role Of O(2) and to construct a scheme of preferential routes occurring in the interaction of EB-PANI with Fe(III) or Cu(II). Solutions of 4.0 mmol L(-1) EB-PANI with 0.8, 2.0 and 20 mmol L(-1) Fe(III) or Cu(II) ions in NMP were investigated and the main observed reactions were EB-PANI oxidation to pernigraniline (PB-PANI) and EB-PANI doping process by pseudo-protonation, or by a two-step redox process. In the presence Of O(2), PB-PANI is observed in all Fe(III)/EB solutions and EB-PANI doping only occurs in solutions with high Fe(III) concentrations through pseudo-protonation. On the other hand, emeraldine salt (ES-PANI) is formed in all Fe(III)/EB solutions under N(2) atmosphere and, in this case, doping occurs both by the pseudo-protonation and two-step redox mechanisms. In all Cu(II)/EB solutions PB-PANI is formed both in the presence and absence of O(2), and only for solutions with high Cu(II) concentrations doping process occurs in a very low degree. The most important result from EPR spectra was providing evidence for redox steps. The determined Cu(II) signal areas under oxygen are higher than under N(2) and, further. the initial metal proportions (1:2:20) are maintained in these spectra, indicating that Cu(I) formed are re-oxidized by O(2) and. so, Cu(II) ions are being recycled. Consistently, for the solutions prepared under nitrogen, the corresponding areas and proportions in the spectra are much lower, confirming that a partial reduction of Cu(II) ions actually occurs. (C) 2009 Elsevier B.V. All rights reserved.

Pre-emptive epidural ketamine or S(+)-ketamine in post-incisional pain in dogs: A comparative study

Objective-To compare the pre-emptive analgesic effects of epidural ketamine or S(+)-ketamine on post-incisional hyperalgesia.Study Design-Prospective randomized study.Animals-Twenty-four mongrel dogs (1-5 years, weighing 11.9 +/- 1.8 kg).Methods-Dogs were anesthetized with propofol (5 mg/kg intravenously) and a lumbosacral epidural catheter was placed. Dogs were randomly allocated to 3 groups, each with 8 dogs. The control group (CG) was administered saline solution (0.3 mL/kg); the ketamine group (KG) ketamine (0.6 mg/kg); and the S(+)-ketamine group (SG) S(+)-ketamine (0.6 mg/kg). The final volume was adjusted to 0.3 mL/kg in all groups. Five minutes after the epidural injection a surgical incision was made in the common pad of the right hind limb and was immediately closed with simple interrupted nylon suture. Respiratory (RR) and heart (HR) rates, rectal temperature (7, sedation (S), lameness score, and mechanical nociceptive threshold by von Frey filaments were evaluated before the propofol anesthesia and at 15, 30, 45, 60, 75, and 90 minutes and then at 2, 4, 6, 8, 12, and 24 hours after epidural injection.Results-There were no differences in RR, HR, T, or S between groups. Motor blockade of the hind limbs was observed during 20 +/- 3.6 minutes in KG and during 30.6 +/- 7.5 minutes in SG (mean SD). Mechanical force applied to obtain an aversive response was higher from 45 minutes to 12 hours in KG and from 60 to 90 minutes in SG, when compared with CG.Conclusions-Pre-emptive epidural ketamine induced no alterations in RR and FIR, and reduced post-incisional hyperalgesia for a longer time than did S(+) ketamine.Clinical Relevance-Although anesthetic and analgesic potency of S(+) ketamine is twice that of ketamine, the racemic form is seemingly better for post-incisional hyperalgesia. (C) Copyright 2004 by the American College of Veterinary Surgeons.

LC Assay for Ciprofloxacin Hydrochloride Ophthalmic Solution

The objective of the current study was to develop and subsequently validate a simple, sensitive and precise reversed-phase LC method for the determination of ciprofloxacin hydrochloride in ophthalmic solution form. The chromatographic separation of ciprofloxacin hydrochloride was achieved on a Symmetry Waters C(18) column using UV detection at 275 nm. The optimized mobile phase consisted of 2.5% acetic acid solution: methanol:acetonitrile (70:15:15, v/v/v). The proposed method provided linear responses within the concentration range 1.0-6.0 mu g mL(-1) for ciprofloxacin hydrochloride. Correlation coefficient (r) for the ciprofloxacin hydrochloride was 0.9994. The precision of the method was demonstrated using intra- and inter-day assay RSD% values which were less than 5% in all instances. No interference from any components of pharmaceutical dosage forms was observed.

Teorias f(R) de gravidade na formulação de Palatini

In this dissertation, after a brief review on the Einstein s General Relativity Theory and its application to the Friedmann-Lemaitre-Robertson-Walker (FLRW) cosmological models, we present and discuss the alternative theories of gravity dubbed f(R) gravity. These theories come about when one substitute in the Einstein-Hilbert action the Ricci curvature R by some well behaved nonlinear function f(R). They provide an alternative way to explain the current cosmic acceleration with no need of invoking neither a dark energy component, nor the existence of extra spatial dimensions. In dealing with f(R) gravity, two different variational approaches may be followed, namely the metric and the Palatini formalisms, which lead to very different equations of motion. We briefly describe the metric formalism and then concentrate on the Palatini variational approach to the gravity action. We make a systematic and detailed derivation of the field equations for Palatini f(R) gravity, which generalize the Einsteins equations of General Relativity, and obtain also the generalized Friedmann equations, which can be used for cosmological tests. As an example, using recent compilations of type Ia Supernovae observations, we show how the f(R) = R − fi/Rn class of gravity theories explain the recent observed acceleration of the universe by placing reasonable constraints on the free parameters fi and n. We also examine the question as to whether Palatini f(R) gravity theories permit space-times in which causality, a fundamental issue in any physical theory [22], is violated. As is well known, in General Relativity there are solutions to the viii field equations that have causal anomalies in the form of closed time-like curves, the renowned Gödel model being the best known example of such a solution. Here we show that every perfect-fluid Gödel-type solution of Palatini f(R) gravity with density and pressure p that satisfy the weak energy condition + p 0 is necessarily isometric to the Gödel geometry, demonstrating, therefore, that these theories present causal anomalies in the form of closed time-like curves. This result extends a theorem on Gödel-type models to the framework of Palatini f(R) gravity theory. We derive an expression for a critical radius rc (beyond which causality is violated) for an arbitrary Palatini f(R) theory. The expression makes apparent that the violation of causality depends on the form of f(R) and on the matter content components. We concretely examine the Gödel-type perfect-fluid solutions in the f(R) = R−fi/Rn class of Palatini gravity theories, and show that for positive matter density and for fi and n in the range permitted by the observations, these theories do not admit the Gödel geometry as a perfect-fluid solution of its field equations. In this sense, f(R) gravity theory remedies the causal pathology in the form of closed timelike curves which is allowed in General Relativity. We also examine the violation of causality of Gödel-type by considering a single scalar field as the matter content. For this source, we show that Palatini f(R) gravity gives rise to a unique Gödeltype solution with no violation of causality. Finally, we show that by combining a perfect fluid plus a scalar field as sources of Gödel-type geometries, we obtain both solutions in the form of closed time-like curves, as well as solutions with no violation of causality

Influence of different levels of aluminum on the development of citrus rootstock swingle citrumelo (Citrus paradisi mcf. x Poncirus trifoliata raf.) in nutrient solution

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Low-Resolution Molecular Models Reveal the Oligomeric State of the PPAR and the Conformational Organization of Its Domains in Solution

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

A fluorescence probe study of gemini surfactants in aqueous solution: a comparison between n-2-n and n-6-n series of the alkanediyl-a,w-bis (dimethylalkylammonium bromides)

Two series of alkanediyl-a,w-bis (dimethylalkylammonium bromide (n-2-n and n-6-n; n=8, 10,12, and 16) have been synthesized and their micelles properties studied in aqueous solution using pyrene, pyrenecarboxaldehyde (PCA) and 1,8 anilinonaphtalene sulfonic acid sodium salt (ANS) as fluorescent probes. The micelles from these surfactants have been characterized on the basis of the information provided by micelle-solubilized fluorescent probes. The obtained results indicated that the surfactant concentration at which a marked decrease in l max parameter of pyrenecarboxaldehyde (PCA) occurs corresponds to the CMC determined by conductimetric measurements. Changes in the emission spectra of ANS and PCA observed in the submicellar range for both surfactants series (n-2-n and n-6-n) were interpreted as formation of pre-aggregates. It was found that the dimeric surfactants with long spacer (s= 6) form more hydrated aggregates when compared with those formed by the n-2-n and CnTAB surfactants series. This was attributed to a more difficult packing of n-6-n surfactant molecules to form micelles.

Aggregation behavior of hydrophobically modified dextran in aqueous solution: a fluorescence probe study

Dextrans (M-W = 11.000 and M-w = 40.000) have been modified with 4-hexyl benzoyl chloride and their aggregation behavior was studied in aqueous solution employing the fluorescent probes pyrene and 1,8 anilinonaphtalene sulfonic acid sodium salt (1,8 ANS). The photophysical studies showed that above a critical concentration the derivatives tend to form aggregates having different properties, which depend on both the degree of substitution (alpha) and the molecular weight of the sample. The parameter alpha has a marked effect on the critical aggregation concentrations (CAC) and aggregate proper-ties. Hydrophobic microenvironments can be detected for substituted dextrans having alpha values varying from 0.01 to 0.19. CAC values decreased by two orders and magnitude when the molecular weight increased from 11 to 40 kDa, leading to formation of more apolar aggregates and diminishing by about 30% the polarity of the microenviromnents. Pre-aggregation was evidenced by pyrene excimer emission and intermolecular interactions were responsible by the formation of aggregates leading to solution behaviour similar to that of common surfactants. (C) 2003 Elsevier B.V. Ltd. All rights reserved.

On the symplectic two-form of gravity in terms of Dirac eigenvalues

The Dirac eigenvalues form a subset of observables of the Euclidean gravity. The symplectic two-form in the covariant phase space could be expressed, in principle, in terms of the Dirac eigenvalues. We discuss the existence of the formal solution of the equations defining the components of the symplectic form in this framework. (C) 2002 Published by Elsevier B.V. B.V.

Godel type solution in teleparallel gravity

The stationary cosmological model without closed timelike curves of Godel type is obtained for the ideal dust matter source within the framework of the teleparallel gravity. For a specific choice of the teleparallel gravity parameters, this solution reproduces the causality violating stationary Godel solution in general relativity, in accordance with the teleparallel equivalent of general relativity. The relation between the axial-vector torsion and the cosmic vorticity is clarified. (C) 2004 Elsevier B.V. All rights reserved.

Nonlinear Gravitational Waves: Their Form and Effects

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

On control and synchronization in chaotic and hyperchaotic systems via linear feedback control

This paper presents the control and synchronization of chaos by designing linear feedback controllers. The linear feedback control problem for nonlinear systems has been formulated under optimal control theory viewpoint. Asymptotic stability of the closed-loop nonlinear system is guaranteed by means of a Lyapunov function which can clearly be seen to be the solution of the Hamilton-Jacobi-Bellman equation thus guaranteeing both stability and optimality. The formulated theorem expresses explicitly the form of minimized functional and gives the sufficient conditions that allow using the linear feedback control for nonlinear system. The numerical simulations were provided in order to show the effectiveness of this method for the control of the chaotic Rossler system and synchronization of the hyperchaotic Rossler system. (C) 2007 Elsevier B.V. All rights reserved.

An Optimal Linear Control Design for Nonlinear Systems

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)