Publications

Abstract In recent years flavonoids have attracted a great interest as potential therapeutic drugs against a wide range of diseases. While the antioxidant activity of these natural polyphenolic compounds is well known, their binding to DNA characteristics is not fully understood despite the fact that many of them exert their biological effects by reversibly binding to nucleic acids. The present study aims to investigate the interaction of flavone and four hydroxyflavone isomers with double stranded DNA, occurring in bulk solution. A combination of micro-DSC and UV spectroscopy has been used to study the effect of these compounds and of their structure on the structure and stability of the DNA molecule. The characteristics of DNA thermal denaturation have been used as a measure of the effect of the compounds on the stability of the double helix. Micro-DSC has been used to determine the temperature dependence of the heat capacity of the process of thermal denaturation of DNA in solutions containing flavone and the following hydroxyflavones: 3-hydroxyflavone, 5-hydroxyflavone, 6-hydroxyflavone and 7-hydroxyflavone. The observed enthalpy of transition and the transition temperature of DNA thermal denaturation were determined for each compound. UV thermal denaturation curves were also recorded, under the same experimental conditions as the DSC measurements. The transition temperature values and the thermodynamic parameters of thermal denaturation were determined. Differential scanning calorimetry and ultraviolet spectroscopy measurements have evidenced an interaction between the studied flavones and DNA, showing a stabilization of DNA structure, due mainly to intercalation of the flavones. The results also show a noteworthy effect of the structure of the hydroxyflavone isomers on this stabilization.

Abstract A static method was used to measure the vapor pressures of crystalline and liquid phases of benzamide, N-methylbenzamide, and N,N-dimethylbenzamide, in the temperature ranges (344.8 to 438.2) K, (322.9 to 388.4) K, and (297.0 to 361.7) K, respectively. The vapor pressures of the crystalline phase of benzamide were also measured using the Knudsen effusion method in the temperature range (324.1 to 344.2) K. From the experimental results, the standard molar Gibbs energies and enthalpies of sublimation and of vaporization, at T = 298.15 K, and the triple points coordinates (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 results enabled the determination of the hydrogen bond enthalpies in the studied compounds.

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.