Publications

Abstract A project focused on the discovery of new chemical entities (NCEs) as AR ligands that incorporate a benzo-gamma-pyrone [(4H)-1-benzopyran-4-one] substructure has been developed. Accordingly, two series of novel chromone carboxamides placed at positions C2 (compounds 2-13) and C3 (compounds 15-26) of the gamma-pyrone ring were synthesized using chromone carboxylic acids (compounds 1 or 14) as starting materials. From this study and on the basis of the obtained structure-activity relationships it was concluded that the chromone carboxamide scaffold represent a novel class of AR ligands. The most remarkable chromones were compounds 21 and 26 that present a better affinity for A(3)AR (K-i = 3680 nM and K-i = 3750 nM, respectively). Receptor-driven molecular modeling studies provide information on the binding/selectivity data of the chromone. The data so far acquired are instrumental for future optimization of chromone carboxamide as a selective A(3)AR antagonist.

Abstract A novel mitochondria-targeted antioxidant (TPP-OH) was synthesized by attaching the natural hydrophilic antioxidant caffeic acid to an aliphatic lipophilic carbon chain containing a triphenylphosphonium (TPP) cation. This compound has similar antioxidant activity to caffeic acid as demonstrated by measurement of DPPH/ABTS radical quenching and redox potentials, but is significantly more hydrophobic than its precursor as indicated by the relative partition coefficients. The antioxidant activity of both compounds was intrinsic related to the ortho-catechol system, as the methoxylation of the phenolic functions, namely in TPP-OCH3 and dimethoxycinnamic acid, gave compounds with negligible antioxidant action. The incorporation of the lipophilic TPP cation to form TTP-OH and TPP-OCH3 allowed the cinnamic derivatives to accumulate within mitochondria in a process driven by the membrane potential. However, only TPP-OH was an effective antioxidant: TPP-OH protected cells against H2O2 and linoleic acid hydroperoxide-induced oxidative stress. As mitochondrial oxidative damage is associated with a number of clinical disorders, TPP-OH may be a useful lead that could be added to the family of mitochondria-targeted antioxidants that can decrease mitochondrial oxidative damage.

Abstract Hydroxycinnamic acids (HCAs) are phenolic compounds present in dietary plants, which possess considerable antioxidant activity. In order to increase the lipophilicity of HCAs, with the aim of improving their cellular absorption and expansion of their use in lipophilic media, methyl, ethyl, propyl and butyl esters of caffeic acid and ferulic acid have been synthesized. All caffeate esters had a slightly lower DPPH IC50 (13.5-14.5 mu M) and higher ferric reducing antioxidant power (FRAP) values (1490-1588 mM quercetin/mole [mMQ/mole]) compared to caffeic acid (16.6 mu M and 1398 mMQ/mole, respectively) in antioxidant assays. In contrast, ferulate esters were less active in DPPH (56.3-74.7 mu M) and FRAP assays (193-262 mMQ/mole) compared to ferulic acid (44.6 mu M and 324 mMQ/mole, respectively). Redox properties of HCAs were in line with their antioxidant capacities, so that compounds with higher antioxidant activities had lower oxidation potentials. Measurement of partition coefficients disclosed the higher lipophilicity of the esters compared to parent compounds. All esters of caffeic acid significantly inhibited hydrogen peroxide-induced neuronal PC12 cell death assessed by MTT assay at 5 and 25 mu M. However, caffeic acid, ferulic acid and ferulate esters were not able to protect the cells. In conclusion, these findings suggest that alkyl esterification of some HCAs augments their antioxidant properties as well as their lipophilicity and as a consequence, improves their cell protective activity against oxidative stress. These compounds could have useful applications in conditions where oxidative stress plays a pathogenic role.

Abstract The vapor pressures of imidazole, N-methylimidazole and of their dichloro and dicyano substituted compounds were measured at different temperatures, in the crystalline phase for two of them, and in crystalline and liquid phases for the other four. From these measurements, enthalpies and standard entropies of sublimation and vaporization were derived. The results allowed the determination of the triple points (p, T) coordinates of the four compounds studied in both condensed phases as well as the calculation of their enthalpy of fusion. Enthalpies and temperatures of fusion were also determined using d.s.c. The experimental results enabled the estimation of the enthalpy of the intermolecular N-H center dot center dot center dot N bonds in the imidazoles studied.

Abstract A static method based on capacitance gauges was used to measure the vapor pressures of the condensed phases of the methyl esters of the three aminobenzoic acids. For methyl o-aminobenzoate the vapor pressures of the liquid phase were measured in the range (285.4 to 369.5) K. For the meta and para isomers vapor pressures of both crystalline and liquid phases were measured in the ranges (308.9 to 376.6) K, and (332.9 to 428.0) K, respectively. Vapor pressures of the latter compound were also measured using the Knudsen effusion method in the temperature range (319.1 to 341.2) K. From the dependence of the vapor pressures on the temperature, the standard molar enthalpies and entropies of sublimation and of vaporization were derived. Differential scanning calorimetry was used to measure the temperatures and molar enthalpies of fusion of the three isomers. The results enabled the estimation of the enthalpy of the intermolecular (N-H center dot center dot center dot O) hydrogen bond in the crystalline methyl p-aminobenzoate. A correlation relating the temperature of fusion and the enthalpy and Gibbs energy of sublimation of benzene, methyl benzoates and benzoic acids was derived.

Abstract Synthesis, characterization, and the optical behavior of CdS quantum dots nanoparticles, confined in zeolites, following a new synthesis approach in different natural zeolites mordenite, clinoptilolite, and syntheticZSM-5, were carried out. The composite materials are characterized by x-ray diffraction, Fourier transmission infrared spectroscopy, energy dispersive, scanning and transmission electron microscopy. After CdS-QDs formation, the synthesized materials become fluorescent with emission wavelengths (average and standard deviation of the maximum wavelength; full width of half maximum): Mordenite-CdS QDs (628 +/- 5 nm; 272 nm); clinoptilolite-CdS QDs (585 +/- 8 nm; 284 nm), and ZSM-5-CdS QDs (579 +/- 4 nm; 214 nm). [Supplemental materials are available for this article. Go to the publisher's online edition of the Journal of Dispersion Science and Technology to view the free supplemental file.]

Abstract Synthesis, characterization, and the optical behavior of CdS quantum dots nanoparticles were studied confined in clays. An alternative synthesis approach in different natural clays K-10 bentonite, Na-montemorillonite, halloysite, and saponite was carried out. The composite materials were characterized by XRD and FTIR spectroscopy, energy dispersive, scanning, and transmission electron microscopy. After CdS-QDs formation, the synthesized materials became fluorescent with emission wavelengths (average and standard deviation of the maximum wavelength; full width of half maximum): K-10 bentonite-CdS (590 +/- 5 nm; 183 nm); Na-montmorillonite-CdS (550 +/- 3 nm; 219 nm); saponite-CdS (550 +/- 5 nm; 219 nm), and halloysite-CdS (590 +/- 8 nm; 185 nm). (Supplemental materials are available for this article. Go to the publisher's online edition of the Journal of Dispersion Science and Technology to view the free supplemental file.)

Abstract The ability of pine bark and almond shells to remove bisphenol A (BPA) from aqueous solutions was evaluated. Samples of these traditional agro-forestry by-products were milled, sieved into different particle size fractions (0.10-0.15 and 1.5-2.0 mm) and submitted to two different types of treatment. Sorption experiments were conducted in a batch system at room temperature and natural pH. Sorption equilibrium was attained after 48 h for all systems under study. Bisphenol A was adsorbed more effectively on the smaller particles of the sorbents. Pine bark and almond shell pretreated with formaldehyde presented higher sorption efficiency (95%), followed by almond shell (87%) and pine bark (82%) washed with hot water. All the sorption isotherms were found to fit a Freundlich equation, with correlation coefficients (R-2) between 0.823 and 0.989. The sorption coefficient (K-F) ranged from 0.06 to 0.74 (mg(1-1/n).L-1/n.g(-1)). These results indicate that utilisation of both materials as an alternative sorbent for the removal of bisphenol A from contaminated waters is promising because they are available in large amounts and have an acceptable cost-efficiency ratio when compared with traditional adsorbents.