Relationship between Hammett's parameters and in silico density functional with tandem mass ESI-CID fragmentation: Dihydropyridines as prototypes.

Over the years, with the instrumental analysis evolution, the relationships between the carried-out results with the data of theoretical analysis in silico and the Hammett's parameters have been reported. They have been very useful for chemical characterization of small organic molecules. Thus, this work aims at showing the feasibility and limitations for Hammett's and density functional theory applications in electrospray ionization-collision-induced dissociation (ESI-CID) fragmentation provision. For this, 13 dihydropyrimidinones para, meta, and orto monosubstituted were studied using ESI and CID in positive mode. As a result, it was observed that the main fragmentation includes the isocyanate and ethanol loses at low energy. Nevertheless, at higher energies, radical ions formed by McLafferty rearrangement were observed. The Hammett plots were correlated fragmentation profiles, showing good linearity for the [M + H]+ , which does not occur to radical ions and carbocation's. These tendencies had demonstrated that the stability of protonate and activation energy of secondary ions changes with the pKa. The density functional theory studies indicated that, both nitrogen atoms in the dihydropyrimidinone's prototypes are capable of being protonated. However, the activation energy of fragmentation products is not changed. Therefore, this work has shown information, which can be useful to understand tandem mass spectrometry in ESI-CID conditions for small organic molecules series. This is the first step for normalization of fragmentation pathway.

Antifungal susceptibility, exoenzyme production and cytotoxicity of novel oximes against Candida.

Novel oximes were synthesized, their in vitro antifungal activity against Candida was evaluated and their cytotoxicity was determined. The procedure used for the synthesis of the oximes is aligned with the current green chemistry trend; water is employed as the solvent in this reaction. The minimum inhibitory and minimum fungicidal concentrations of the oximes were evaluated using the CLSI M27-A3 method. The influence of these compounds on the inhibition of the production of hydrolytic enzymes, phospholipase and proteinase by Candida was also investigated. The compounds showed a good ability to inhibit phospholipase, with a 50 % reduction in most cases. However, the tested compounds did not affect proteinase. The current results showed a substantial reduction in the phospholipase production, which suggests that compounds of this class may interfere with host infection and disease progression. The oximes examined showed lower fungicidal activities than fluconazole but interfered significantly with the expression of phospholipase. Some of the oximes included in this study could be a suitable matrix for the development of novel antifungal compounds.

Self-etching dental adhesive containing a natural essential oil: anti-biofouling performance and mechanical properties.

This study assessed the anti-biofouling performance of an experimental adhesive system containing a naturally occurring essential vegetable oil and examined the following physical and mechanical properties: water sorption (WS) and solubility (SL), microtensile bond strength to dentin (µTBS), and degree of conversion. The following six groups were tested: a self-etching experimental adhesive containing refined essential oil from the seeds of the Butia capitata tree (EAO); an oil-free version of the experimental adhesive (EANO); one group without adhesive as the control (C); and the three following commercial self-etching adhesives: Clearfil Protect Bond (CPB), Clearfil SE Bond, and Adper SE Plus. The antibacterial effect was estimated by microbiological culture on selective/non-selective media, and the results expressed as colony-forming units per unit weight of dry biofilm (CFU mg(-1)). The data were submitted to ANOVA and Tukey's post hoc test (α = 0.05). After 24 h, pH changes were similar in the storage medium of all tested adhesive systems. EAO showed similar levels of antimicrobial activity in a model biofilm microcosm as the commercial self-etching adhesive CPB. Both were effective against total microorganisms, aciduric bacteria, lactobacilli, and Streptococcus mutans. WS and SL were not affected by the presence of the essential oil; the values of EAO were similar to or less than those of commercial equivalents. The incorporation of an essential oil into an experimental adhesive did not influence its monomer conversion result. Immediate µTBS values of EAO and EANO were similar and were greater than those of commercial equivalents. After storage for 6 months, the µTBS of the EAO decreased significantly and became similar to the values of commercial equivalents, while the strength of the EANO was not affected.