O comportamento eletroquímico em função da estrutura de uma série de derivados dos ácidos cafeico e ferúlico, assim como de seus precursores catecol e guaiacol, eletroquimicamente ativos, foi avaliado por voltametria cíclica. Os resultados revelaram que as condições experimentais são a chave para as mudanças no mecanismo de oxidação do guaiacol e ácido ferúlico. A oxidação eletroquímica dos derivados amida do ácido ferúlico revelou que o átomo de nitrogênio desempenha um papel importante na derivatização da superfície do eletrodo. Além disso, a atividade sequestradora de radicais dos compostos, avaliada através da porcentagem de inibição do radical 2,2'-difenil-1-picril-hidrazila, mostrou uma boa correlação com os potenciais de oxidação.We studied the electrochemical behaviour as a function of the structure of a series of caffeic and ferulic acids derivatives as well as their corresponding redox moieties catechol and guaiacol by cyclic voltammetry. Results revealed that the medium is key for changes in the oxidation mechanism of guaiacol and ferulic acid. Electrochemical oxidation of the ferulic acid amide derivatives revealed that the nitrogen atom plays an important role in the derivatization of the electrode surface. In addition, radical scavenging activity of the compounds evaluated through the percentage of inhibition of the 2,2'-diphenyl-1-picrylhidrazyl radical showed a good relationship with the oxidation potentials.

The electrochemical oxidation in DMSO of four new derivatives of caffeic acid (CA), two dimeric amides and two dimeric esters, is reported in this article. Although all of them contain two caffeoyl electroactive moieties in their structures, small differences in the connectors result in interesting changes in the electrochemical behaviour of this type of compound. Voltammograms of both esters do not show appreciable differences between them; however, an electrografting process occurs during the electrochemical oxidation of one of them, which suggests that the identity of the connector has an influence on the ability of the diesters to interact with the electrode surface. On the other hand, voltammograms of dimeric amides were more complex than those corresponding to dimeric esters. Electronic effects of diamine connectors seem to be related to the fact that caffeoyl moieties suffer from separate oxidation processes in both compounds. In contrast to their ferulic acid (FA) analogues, which have been studied by our group before, CA dimeric amides do not interact in an appreciable way with the electrode surface. In addition, a relationship between the oxidation potential and the inhibition percentage of the DPPH (2,2'-diphenyl-1-picrylhydrazyl) radical was not observed for the symmetrical CA derivatives studied here. However, the molecular flexibility seems to play a very important role in the Free Radical Scavenging Activity (FRSA) of this type of compound.

No abstract

In this study the effect of pollen source (mesquite and catclaw) on the sensory characteristics (appearance, color, aroma, taste, consistency and visible impurities), and physicochemical properties of raw propolis, and the phenolic content and biological activities of propolis extracts (PEs) was determined. The phenolic composition of PEs was determined by the total phenolic (TPC), flavone and flavonol (FFC), and flavanone and dihydroflavonol content (FDC). The individual phenolic components were analyzed by HPLC-DAD. The antioxidant activity was determined by the ferric-reducing power (FRAP) and free-radical scavenging activity (FRS). The antibacterial activity was evaluated against Gram-positive (Staphylococcus aureus and Listeria innocua) and Gram-negative (Echerichia coli and Salmonella thyphimurium) bacteria. The results showed that sensory characteristic and physicochemical properties of mesquite and catclaw propolis complied with international quality regulations. Fifteen phenolic compounds were identified, of which pinocembrin, naringenin, galangin, chrysin and quercetin were found a high concentration (> 3 mg/g). Mesquite propolis had the highest phenolic content (TFC and FDC), as well as antioxidant activity (> 2.5 mg Fe (II) equivalent/g; > 40% of DPPH radical inhibition) and antibacterial activity against Gram-positive bacterias in the order S. aureus > L. innocua (> 50% of inhibition for both bacterias at 500 µg/mL). These results indicating that pollen source affect the sensory characteristics and physicochemical properties of propolis, as well as the biological activity of their extracts.

The transport of hydrophobic drugs in the human body exhibits complications due to the low solubility of these compounds. With the purpose of enhancing the bioavailability and biodistribution of such drugs, recent studies have reported the use of amphiphilic molecules, such as phospholipids, for the synthesis of nanoparticles or nanocapsules. Given that phospholipids can self-assemble in liposomes or micellar structures, they are ideal candidates to function as vehicles of hydrophobic molecules. In this work, we report mesoscopic simulations of nanoliposomes, constituted by lecithin and coated with a shell of chitosan. The stability of such structures and the efficiency of the encapsulation of capsaicin, as well as the internal and superficial distribution of capsaicin and chitosan inside the nanoliposome, were analyzed. The characterization of the system was carried out through density maps and the potentials of mean force for the lecithin-capsaicin, lecithin-chitosan, and capsaicin-chitosan interactions. The results of these simulations show that chitosan is deposited on the surface of the nanoliposome, as has been reported in some experimental works. It was also observed that a nanoliposome of approximately 18 nm in diameter is stable during the simulation. The deposition behavior was found to be influenced by a pattern of N-acetylation of chitosan.