Biological Oxidations and Nitrations Promoted by the Hemin-Aß16 Complex.

Both ß-amyloid (Aß) peptides and oxidative stress conditions play key roles in Alzheimer's disease. Hemin contributes to the development of the disease as it possesses redox properties and its level increases in pathological conditions or traumatic brain injuries. The aim of this work was to deepen the investigation of the reactivity of the hemin-Aß16 complex, considering its ability to catalyze oxidation and nitration reactions. We performed kinetic studies in the presence of hydrogen peroxide and nitrite with phenolic and catechol substrates, as well as mass spectrometry studies to investigate the modifications occurring on the peptide itself. The kinetic constants were similar for oxidation and nitration reactions, and their values suggest that the hemin-Aß16 complex binds negatively charged substrates with higher affinity. Mass spectrometry studies showed that tyrosine residue is the endogenous target of nitration. Hemin degradation analysis showed that hemin bleaching is only partly prevented by the coordinated peptide. In conclusion, hemin has rich reactivity, both in oxidation and nitration reactions on aromatic substrates, that could contribute to redox equilibrium in neurons. This reactivity is modulated by the coordination of the Aß16 peptide and is only partly quenched when oxidative and nitrative conditions lead to hemin degradation.

Synthesis, Characterization and Application of a MIP-polyHIPE for Selective Extraction of Angiotensin II Receptor Antagonists Residues in Natural Waters.

Polymers via high internal phase emulsion (polyHIPEs) were molecularly imprinted with Irbesartan, an antihypertensive drug belonging to the class of angiotensin II receptor antagonists (sartan drugs), chosen for the proof-of-concept extraction of hazardous emerging contaminants from water. Different analyte-functional monomer molar ratios (1:100, 1:30 and 1:15) were investigated, and the MIP polyHIPEs have been characterized, parallel to the not imprinted polymer (NIP), by batch sorption experiments. The material with the highest template-functional monomer ratio was the best for Irbesartan removal, showing a sorption capacity fivefold higher than the NIP. Regarding the adsorption kinetics, the analyte-sorbent equilibrium was reached after about 3 h, and the film diffusion model best fitted the kinetic profile. Selectivity was further demonstrated by testing Losartan, another sartan drug, observing a fourfold lower sorption capacity, but still higher than that of NIP. The polymers were also synthesized in cartridges for solid-phase extraction (SPE), which was helpful for evaluating the breakthrough curves and performing pre-concentrations. These have been done in tap and river water samples (100-250 mL, 15-500 µg L-1 Irbesartan), obtaining quantitative sorption/desorption on the MIP-polyHIPE (RSD < 14%, n = 3). The NIP provided a recovery of just around 30%, evidence of partial uptake of the target from water.

Introduction of a triphenylamine substituent on pyridyl rings as a springboard for a new appealing brightly luminescent 1,3-di-(2-pyridyl)benzene platinum(II) complex family.

The preparation and characterization of three new complexes, namely [Pt(1,3-bis(4-triphenylamine-pyridin-2-yl)-4,6-difluoro-benzene)Cl] ([PtL1Cl]), [Pt(1,3-bis(4-triphenylamine-pyridin-2-yl)-5-triphenylamine-benzene)Cl] ([PtL2Cl]), and [Pt(1,3-bis(4-triphenylamine-pyridin-2-yl)-5-mesityl-benzene)Cl] ([PtL3Cl]), is reported. All of them are highly luminescent in dilute deaerated dichloromethane solution (Φlum = 0.88-0.90, in the yellow-green region; the λmax,em in nm for the monomers are: 562, 561 and 549 for [PtL1Cl], [PtL2Cl] and [PtL3Cl], respectively).[PtL1Cl] is the most appealing, being characterized by a very long lifetime (103.9 µs) and displaying intense NIR emission in concentrated deaerated solution (Φlum = 0.66) with essentially no "contamination" by visible light < 600 nm. This complex allows the fabrication of both yellow-green and deep red/NIR OLEDs; OLED emissions are in the yellow-green (CIE = 0.38, 0.56) and deep red/NIR (CIE = 0.65, 0,34) regions, for [PtL1Cl] 8 wt% (with 11% ph/e EQE) and pure [PtL1Cl] (with 4.3% ph/e EQE), respectively.