Publications

Abstract Halogenated benzenes form a class of pollutants with a huge number of members - 1504 distinct benzene compounds, where one or more hydrogen atoms are replaced by halogens, may exist theoretically. This study presents a user friendly method for accurate prediction of vapor pressures and enthalpies of vaporization, at 298.15 K, of any mono or poly halobenzene compound. The derived equations for the prediction of those vaporization properties depend just on the number of each constituent halogen atom. This is a consequence of the absence of intramolecular interactions between the halogen atoms, revealed after examining vaporization results of ca. 40 halogenated benzenes. In order to rationalize the estimation equations, the contribution of the halogen atoms for the referred to above properties of vaporization was decomposed into two atomic properties - the volume and electron affinity. Extension of the applicability of the estimation method to substituted benzenes containing other substituent groups beyond halogen atoms as well as to some polycyclic aromatic species was tested with success.

Abstract In the present work we synthesized a selected series of hydroxylated 3-phenylcoumarins 5-8, with the aim of evaluating in detail their antioxidant properties. From an in depth study of the antioxidant capacity data (ORAC-FL, ESR, CV and ROS inhibition) it was concluded that these derivatives are very good antioxidants, with very interesting profiles in all the performed assays. The study of the effect of the number and position of the hydroxyl groups on the antioxidant activity was the principal aim of this study. In particular, 7-hydroxy-3-(3'-hydroxy)phenylcoumarin (8) proved to be the most active and effective antioxidant of the selected series in four of the performed assays (ORAC-FL = 11.8, capacity of scavenging hydroxyl radicals = 54%, Trolox index = 2.33 and AI(30) index = 0.18). However, the presence of two hydroxyl groups on this molecule did not increase greatly the activity profile. Theoretical evaluation of ADME properties of all the derivatives was also carried out. All the compounds can act as potential candidates for preventing or minimizing the free radical overproduction in oxidative-stress related diseases. These preliminary findings encourage us to perform a future structural optimization of this family of compounds.

Abstract We report a nanocomposite of ZnS:Mn quantum dots and a third generation PAMAM-OH dendrimer (ZnS:Mn@PAMAM-OHG=3) which was rationalized to be used as ratiometric nanosensor for Cd2+ in aqueous solution. The nanoparticles exhibited a bright yellow-orange emission with peaks at 448 and 595 nm. The structure of ZnS:Mn was not changed after coupling with PAMAM-OH, which was evidenced by the analysis of the emission spectra of the compounds. The results confirm that the prepared fluorescence nanoparticles could selectively detect Cd2+ in aqueous solution with a limit of detection of 24.34 mu M and RSD 4.07%, obtained by using the ratio I-448/I-595. The method was applied to different water samples.

Abstract Firefly bioluminescence is a phenomenon that attracts attention from the research community because of complex challenges for fundamental investigation, as well as diverse opportunities for practical application. Here we have studied the potential deprotonation of firefly oxyluciferin by using a theoretical approach in an enzymatic-like microenvironment in chemiexcited proton transfer involving adenosine 5'-monophosphate. We have uncovered a reaction route that links the evidence that the light-emitter is an anionic molecule while it is chemiexcited in its neutral form. Moreover, the results indicated that the anionic bioluminophore is the enolate anion and not the ketonic one. Further calculations supported this identification of the light-emitter: the spectrum of resulting enolate anion covers the entire yellow-green/red bioluminescence range, which is in line with the experimental findings regarding firefly multicolor bioluminescence.

Abstract Cyclooxygenase (COX) enzymes are involved in inflammation and cancer. Nine derivatives of hydroxycinnamic acid including ethyl and diethyl esters were synthesized and tested as COX inhibitors in a whole blood assay. Esterification improved COX-1 and COX-2 inhibitory activities of the derivatives. Ethyl esters were more effective against COX-1 and the most potent one was caffeic acid ethyl ester. Interestingly, diethyl esters showed selectivity towards COX-2; the most active compound was caffeic acid diethyl ester (CA-DE) with 88.5 and 30.5% inhibition against COX-2 at 100 and 20 mu M, respectively, while it was almost inactive against COX-1. Docking studies showed that CA-DE forms 3 hydrogen bonds with the active site of COX-2 (4-OH center dot center dot center dot OH-Tyr355, 4-OH center dot center dot center dot NH-Arg120 and C=O center dot center dot center dot OH-Tyr385), while it forms only the first two bonds with COX-1. Furthermore, the Val523 residue in COX-2 provides a wide hydrophobic pocket, which would accommodate diethyl esters. The present approach inspired by a natural scaffold provides an asset for the generation of new chemical entities endowed with selective COX-2 inhibitory activity.

Abstract Pollen of Betula pendula, Ostrya carpinifolia, and Carpinus betulus was exposed in vitro to relatively low levels of the air pollutants, namely carbon monoxide, ozone, and sulfur dioxide. The allergenicity of the exposed pollen was compared with that of non-exposed pollen samples to assess if air pollution exposition affects the allergenicity potential of pollen. The immunodetection assays indicated higher IgE recognition by all sera of allergic patients to the pollen protein extracts in all exposed samples in comparison to the non-exposed samples. These results show that the pollen exposition to low pollutants' levels induces increased allergic reaction to sensitized individuals.

Abstract Magnesium is an essential mineral in human metabolism, and is the second most abundant intracellular cation and the fourth most abundant in the human body. Magnesium has a large variety of biological functions, including being a cofactor for over 300 enzymes, mainly involving phosphorylation of proteins and nucleic acids. Low levels of magnesium in the body can develop during different illnesses, such as diabetes (type 2), metabolic syndrome, cardiac arrhythmias, and muscular constriction. The present review shows the advances in analytical chemistry based on sensor systems to quantify the concentration of magnesium in different biological samples, plasma, serum, or urine, that are relevant to human health.

Abstract BACKGROUNDStimuli responsive imprinted hydrogel micro-particles were prepared using reversible addition-fragmentation chain transfer polymerization for targeting genotoxic impurity aminopyridine in aqueous environment using a continuous flow micro-reactor. RESULTSThe feasibility of operation with a continuous flow micro-reactor for particles production was demonstrated. A comparative evaluation was carried out between batch and micro-reactor produced imprinted and non-imprinted hydrogels. Experimental results proved that molecular imprints generated by free radical polymerization and controlled radical polymerization showed outstanding performance in adsorption behavior: the q value estimate was about 1000 times higher than the value presented by other researchers. Solid phase extraction results further evidenced the promising imprinting with hydrogels using free radical polymerization and controlled radical polymerization by retaining c. 100% of 3-aminopyridine. The imprinting factor of 4.3 presented in this research appears to be the best value shown so far. CONCLUSIONThe imprinted materials were successfully prepared both in batch and with a continuous flow micro-reactor. The inclusion of a reversible addition-fragmentation chain transfer agent in controlled radical polymerization was important in optimizing the experimental conditions in the continuous microfluidic approach. Though the reversible addition-fragmentation chain transfer agent was very useful in controlling the reaction kinetics, imprinted micro-particles showed the existence of both non-specific and imprinted sites. It is worth extending this work to demonstrate the impact of reversible addition-fragmentation chain transfer agents in molecular imprinting, considering also operation in a continuous flow micro-reactor to obtain tailored smart hydrogel particles. (c) 2015 Society of Chemical Industry

Abstract In the current work, the complexes formed between triplet vinyl nitrene ((CH2CHN)-C-3) and some Lewis acids YA (LiH, LiF, BeH2, BeF2, BH3, BF3, ClH, ClF, HCl, HF) have been investigated through calculations of the electronic structure. These calculations have been carried out in order to determine the energetic stability of the N center dot center dot center dot Y (with Y = Li, Be, B, Cl, H) interactions and also to understand their chemical nature. Quantum chemical calculations predict that the molecular complexes (CH2CHN)-C-3 center dot center dot center dot Y-A are always more stable than the separated (CH2CHN)-C-3 and Y-A species. The interaction energies range from -0.98 kcal mol(-1) (in CH2=CHN center dot center dot center dot ClH) to -39.03 kcal mol(-1) (in CH2=CHN center dot center dot center dot BH3) at the CCSD(T)/6-311++G(2d,2p) level of theory. Accordingly, some of these complexes may serve to experimentally detect and characterize the elusive triplet vinyl nitrene species. Moreover, AIM theory, in particular the L(r) = -A1/4a double dagger(2) rho(r) function, reveals that the N center dot center dot center dot Y interactions established between the electron lone pair of the nitrogen atom and the charge density depletion region of the Y atom are mainly of electrostatic character.

Abstract Complex self-assembled structures can be built up in aqueous media by making use of non-covalent interactions between small organic molecules and conventional amphiphiles. The macrocycle p-sulfonatocalix[4]arene (SC4) is a known receptor for organic ammonium cations in aqueous solution, showing strong binding ability for those guests and selectivity for several amino acids. Previous studies have shown that this type of water-soluble calixarenes are able to modify the aggregation behavior of surfactants. Here, we explore the interactions and morphologies present in mixtures of SC4 and a cationic serine-based surfactant, resorting to surface tension, light microscopy, cryo-scanning electron microscopy and nuclear magnetic resonance studies. Complexation of the amino acid-based surfactant by the calixarene leads initially to mixed micelle formation and a significant lowering of the critical micelle concentration with respect to the neat surfactant even for very low content of SC4 (up to 1.4 mol%). Interestingly, as the SC4 fraction in the system is gradually increased (about 2-6 mol%), highly flexible tubular structures and vesicles are assembled. The observed self-assembly is rationalized in terms of electrostatic complexation between the two co-solutes and the preferred packing of the supramolecular complexes formed.