Publications

Abstract A static method was used to measure the vapor pressures of crystalline and liquid phases of ortho-, meta-, and para-fluorobenzamides, in the temperature ranges (318.0 to 412.2) K, (336.8 to 432.0) K, and (344.8 to 437.8) K, respectively. The vapor pressures of the crystalline phase of the ortho- and meta-isomers were also measured using the Knudsen effusion method in the pressure ranges (0.1 to 1) Pa. From the experimental results, the standard molar Gibbs energies and enthalpies of sublimation and of vaporization, at T = 298.15 K, and the triple-point results (p, T) for the three compounds were derived. The temperatures and molar enthalpies of fusion were also determined using differential scanning calorimetry and were compared with the values derived from the vapor pressure measurements. The enthalpy of the intermolecular hydrogen bonds N-H center dot center dot center dot O in the studied compounds will be discussed and compared with the values derived for benzamide.

Abstract A new fluorescent sensor for nitric oxide (NO) is presented that is based on its reaction with a non fluorescent substance, reduced fluoresceinamine, producing the highly fluorescent fluoresceinamine. Using a portable homemade stabilized light source consisting of 450 nm LED and fiber optics to guide the light, the sensor responds linearly within seconds in the NO concentration range between about 10-750 mu M with a limit of detection (LOD) of about 1 mu M. The system generated precise intensity readings, with a relative standard deviation of less than 1%. The suitability of the sensor was assessed by monitoring the NO generated by either the nitrous acid decomposition reaction or from a NO-releasing compound. Using relatively high incubation times, the sensor also responds quantitatively to hydrogen peroxide and potassium superoxide, however, using transient signal measurements results in no interfering species.

Abstract The standard (p(0) = 0.1 MPa) molar enthalpies of formation, in the crystalline phase, of five aminomethoxybenzoic acids, at T = 298.15 K, were derived from the standard molar energies of combustion in oxygen, measured by static-bomb combustion calorimetry. Combining these results with literature results of the standard molar enthalpies of sublimation, at T = 298.15 K, the standard molar enthalpies of formation, in the gaseous phase, were derived. Additionally, the enthalpies of formation of the ten possible isomers of aminomethoxybenzoic acid were estimated using accurate Double Hybrid Density Functional Theory (DHDFT) computational methods. The good agreement between the experimental and estimated values of the enthalpies of formation of the five isomers studied experimentally allows us to be confident on the estimated values for the other five isomers. A quantitative evaluation and analysis of the aromatic character of all the studied isomers based on the calculation of Nucleus Independent Chemical Shifts (NICS) was also conducted.

Abstract Aberrantly regulated apoptosis is involved in the pathogenesis of several diseases and defective apoptosis leads to uncontrolled cell proliferation and tumorigenesis. Cancer is an example of a pathologic condition where the normal mechanisms of cell cycle regulation are dysfunctional either by excessive cell proliferation, inhibited/suppressed apoptosis or both. Dietary habits are estimated to contribute to, at least, one third of all human cancers, showing that dietary components can exacerbate or interfere with carcinogenesis. However, several epidemiological studies have revealed that some dietary factors can decrease the risk of different types of cancer. Apoptosis is suggested to be a crucial mechanism for the chemopreventive properties associated with several dietary factors by eliminating potentially deleterious (damaged/mutated) cells. Food, a readily available item, contains several promising chemopreventive agents. Polyphenols are serious candidates since they are responsible for the cancer protective properties of a diet rich in vegetables and fruits: numerous phenolic compounds showed antiproliferative and cytotoxic effects and, more specifically, pro-apoptotic activities, in several cancer cells lines and animal tumor models. The aim of the present review is to analyze and summarize several aspects related to the molecular mechanisms of apoptosis induced by dietary factors with particular emphasis on polyphenols. Dietary factors that can activate cell death signals and induce apoptosis, preferentially in precancerous or malignant cells, and the study of their apoptotic inducing targets can represent a mean to devise new strategies for cancer prevention in the future.

Abstract The synthesis of carbon nanoparticles obtained by direct laser ablation [UV pulsed laser irradiation (248 nm, KrF)] of carbon targets immersed in water is described. Laser ablation features were optimized to produce carbon nanoparticles with dimensions up to about 100 nm. After functionalization with NH2-polyethylene-glycol (PEG(200)) and N-acetyl-L-cysteine (NAC) the carbon nanoparticles become fluorescent with excitation and emission wavelengths at 340 and 450 nm, respectively. The fluorescence decay time was complex and a three-component decay time model originated a good fit (chi = 1.09) with the following lifetimes: tau(1) = 0.35 ns; tau(2) = 1.8 ns; and tau(3) = 4.39 ns. The fluorescence of the carbon dots is sensitive to pH with an apparent PKa = 4.2. The carbon dots were characterized by H-1 NMR and HSQC and the results show an interaction between PEG(200) and the carbon surface as well as a dependence of the chemical shift with the reaction time. The fluorescence intensity of the nanoparticles is quenched by the presence of Hg(II) and Cu(II) ions with a Stern-Volmer constant (pH = 6.8) of 1.3 x 10(5) and 5.6 x 10(4) M-1, respectively. As such the synthesis and application of a novel biocompatible nanosensor for measuring Hg(II) is presented.

Abstract The standard (p(o) = 0.1 MPa) molar enthalpies of formation in the crystalline state of the 2-,3- and 4-hydroxymethylphenols, Delta(f)H(m)(o)(cr) = -(377.7 +/- 1.4) kJ mol(-1), Delta(f)H(m)(o)(cr) = -(383.0 +/- 1.4) kJ mol(-1) and Delta(f)H(m)(o)(cr) = -(382.7 +/- 1.4) kJ mol(-1), respectively, were derived from the standardmolar energies of combustion, in oxygen, to yield CO(2)(g) and H(2)O(l), at T = 298.15 K, measured by static bomb combustion calorimetry. The Knudsen mass-loss effusion technique was used to measure the dependence of the vapour pressure of the solid isomers of hydroxymethylphenol with the temperature, from which the standard molar enthalpies of sublimation were derived using the Clausius-Clapeyron equation. The results were as follows: Delta(g)(cr)H(m)(o) = (99.5 +/- 1.5) kJ mol(-1), Delta(g)(cr)H(m)(o) = (116.0 +/- 3.7) kJ mol(-1) and D(cr)(g)H(m)(o) = (129.3 +/- 4.7) kJ mol(-1), for 2-, 3- and 4-hydroxymethylphenol, respectively. From these values, the standard molar enthalpies of formation of the title compounds in their gaseous phases, at T = 298.15 K, were derived and interpreted in terms of molecular structure. Moreover, using estimated values for the heat capacity differences between the gas and the crystal phases, the standard (p(o) = 0.1 MPa) molar enthalpies, entropies and Gibbs energies of sublimation, at T = 298.15 K, were derived for the three hydroxymethylphenols.

Abstract The Knudsen mass-loss effusion technique was used to measure the vapor pressures at different temperatures of the following aminomethoxybenzoic acids: 2-amino-3-methoxybenzoic acid, between (349.12 and 369.18) K; 2-amino-5-methoxybenzoic acid, between (353.13 and 375.17) K; 3-amino-4-methoxybenzoic acid, between (379.67 and 399.18) K; 3-amino-5-methoxybenzoic acid, between (380.16 and 400.18) K; and 4-amino-3-methoxybenzoic acid, between (373.14 and 395.17) K. From the temperature dependences of the vapor pressure of the crystalline compounds, the standard (p degrees = 10(5) Pa) molar enthalpies and Gibbs energies Of Sublimation, at T = 298.15 K, were derived. The results allowed the estimation of these two thermodynamic properties for two isomers not Studied in this work-2-amino-6-methoxybenzoic acid and 3-amino-2-methoxybenzoic acid. Differential scanning calorimetry was Used to measure the temperature and molar enthalpy of fusion of the studied isomers.

Abstract A series of 6-halo-3-hydroxyphenylcoumarins (resveratrol-coumarins hybrid derivatives) was synthesized in good yields by a Perkin reaction followed by hydrolysis. The new compounds were evaluated for their vasorelaxant activity in intact rat aorta rings pre-contracted with phenylephrine (PE), as well as for their inhibitory effects on platelet aggregation induced by thrombin in washed human platelets. These compounds concentration-dependently relaxed vascular smooth muscle and some of them showed a platelet antiaggregatory activity that was up to thirty times higher than that shown by trans-resveratrol and some other previously synthesized derivatives.

Abstract This paper reports an experimental and theoretical study of the gas phase standard (p(o) = 0.1 MPa) molar enthalpies of formation, at T = 298.15 K, of alpha-alanine (DL) and beta-alanine. The standard (p(o) = 0.1 MPa) molar enthalpies of formation of crystalline alpha-alanine (DL) and beta-alanine were calculated from the standard molar energies of combustion, in oxygen, to yield CO2(g), N-2(g), and H2O(l), measured by static-bomb combustion calorimetry at T = 298.15 K. The vapor pressures of both amino acids were measured as function of temperature by the Knudsen effusion mass-loss technique. The standard molar enthalpies of sublimation at T = 298.15 K was derived from the Clausius-Clapeyron equation. The experimental values were used to calculate the standard (p(o) = 0.1 MPa) enthalpy of formation of alpha-alanine (DL) and beta-alanine in the gaseous phase, Delta H-f(m)o(g), as -426.3 +/- 2.9 and -421.2 +/- 1.9 kJ.mol(-1), respectively. Standard ab initio molecular orbital calculations at the G3 level were performed. Enthalpies of formation, using atomization reactions, were calculated and compared with experimental data. Detailed inspections of the molecular and electronic structures of the compounds studied were carried out.

Abstract Gemini surfactants possess interesting interfacial and aggregation properties that have prompted comprehensive studies and successful applications in a wide variety of fields. However, a systematic study on the effect of gemini tail and spacer length upon the organization of lipid membranes has not been presented so far. In this study, we analyze the action of dicationic alkylammonium bromide gemini surfactants on DPPC liposomes, the latter employed as a model of lipid membranes. Differential scanning calorimetry results indicate that the surfactants presenting shorter tails (12 carbons) induce a decrease in the overall order of the bilayer, while those with longer tails (16 and 18 carbons) lead to the formation of more ordered structures. The respective influence on the degree of lipid order transverse to the bilayer was additionally studied resorting to a detailed fluorescence anisotropy study. In this case, it is observed that among the shorter tail surfactants, those with longer spacers (6 and 10 carbons) are responsible for a more pronounced disrupting effect upon the membrane, especially close to the lipid polar heads. Molecular dynamics simulation supports the most important findings and provides insight into the mechanism that governs this interaction. Accordingly, the interplay between tail and spacer length accounts for the differential vertical positioning of the gemini molecules and atom-density in the core of the bilayer, that provide a rationale for the experimental observations.