Lorenzo Franco

Rosiglitazone Reduces Glucose-Induced Oxidative Stress Mediated by NAD(P)H Oxidase via AMPK-Dependent Mechanism

Objective—Hyperglycemia is the main determinant of long-term diabetic complications, mainly through induction of oxidative stress. NAD(P)H oxidase is a major source of glucose-induced oxidative stress. In this study, we tested the hypothesis that rosiglitazone (RSG) is able to quench oxidative stress initiated by high glucose through prevention of NAD(P)H oxidase activation. Methods and Results—Intracellular ROS were measured using the fluoroprobe TEMPO-9-AC in HUVECs exposed to control (5 mmol/L) and moderately high (10 mmol/L) glucose concentrations. NAD(P)H oxidase and AMPK activities were determined by Western blot. We found that 10 mmol/L glucose increased significantly ROS production in comparison with 5 mmol/L glucose, and that this effect was completely abolished by RSG. Interestingly, inhibition of AMPK, but not PPAR&ggr;, prevented this effect of RSG. AMPK phosphorylation by RSG was necessary for its ability to hamper NAD(P)H oxidase activation, which was indispensable for glucose-induced oxidative stress. Downstream of AMPK activation, RSG exerts antioxidative effects by inhibiting PKC. Conclusions—This study demonstrates that RSG activates AMPK which, in turn, prevents hyperactivity of NAD(P)H oxidase induced by high glucose, possibly through PKC inhibition. Therefore, RSG protects endothelial cells against glucose-induced oxidative stress with an AMPK-dependent and a PPAR&ggr;-independent mechanism.

Synthesis and Photochemical Applications of Processable Polymers Enclosing Photoluminescent Carbon Quantum Dots

Herein, we propose convenient routes to produce hybrid-polymers that covalently enclosed, or confined, N-doped carbon quantum dots (CQDs). We focus our attention on polyamide, polyurea-urethane, polyester, and polymethylmetacrylate polymers, some of the most common resources used to create everyday materials. These hybrid materials can be easily prepared and processed to obtain macroscopic objects of different shapes, i.e., fibers, transparent sheets, and bulky forms, where the characteristic luminescence properties of the native N-doped CQDs are preserved. More importantly we explore the potential use of these hybrid composites to achieve photochemical reactions as those of photoreduction of silver ions to silver nanoparticles (under UV-light), the selective photo-oxidation of benzylalcohol to the benzaldehyde (under vis-light), and the photocatalytic generation of H2 (under UV-light).

Magnetic Properties and Vapochromic Reversible Guest-Induced Transformation in a Bispyrazolato Copper(II) Polymer: an Experimental and Dispersion-Corrected Density Functional Theory Study

Dispersion-corrected density functional theory (DFT-D) calculations, Electron Spin Resonance spectroscopy (EPR), and variable temperature magnetic moment measurements were used to investigate the structure and the electronic/magnetic properties of bispyrazolato-copper(II) coordination polymer and of its hydration product. The Cu(II) ions are antiferromagnetically coupled through the sigma system of the pyrazolate rings in both compounds. Theoretical electron density maps reveal that water molecules interact simultaneously and to a comparable extent with two Cu(II) centers (through the electronegative O end) and two pyrazolate rings (through the partly positively charged H atoms), which is compatible with the observed internuclear distances. DFT-D calculations indicate that low kinetic barriers are involved in the rearrangement of the host structure.

Solar cells based on a fullerene–azothiophene dyad

A power conversion efficiency of 0.37%, under white light of 80 mW cm-2 intensity, was obtained when a fullerene-azothiophene dyad was used as the active layer of a photovoltaic cell.

Spectroscopic Insights into Carbon Dot Systems

The controversial nature of the fluorescent properties of carbon dots (CDs), ascribed either to surface states or to small molecules adsorbed onto the carbon nanostructures, is an unresolved issue. To date, an accurate picture of CDs and an exhaustive structure-property correlation are still lacking. Using two unconventional spectroscopic techniques, fluorescence correlation spectroscopy (FCS) and time-resolved electron paramagnetic resonance (TREPR), we contribute to fill this gap. Although electron micrographs indicate the presence of carbon cores, FCS reveals that the emission properties of CDs are based neither on those cores nor on molecular species linked to them, but rather on free molecules. TREPR provides deeper insights into the structure of carbon cores, where C sp2 domains are embedded within C sp3 scaffolds. FCS and TREPR prove to be powerful techniques, characterizing CDs as inherently heterogeneous systems, providing insights into the nature of such systems and paving the way to standardization of these nanomaterials.

Crystal violet: Study of the photo-fading of an early synthetic dye in aqueous solution and on paper with HPLC-PDA, LC-MS and FORS

The photo-fading of crystal violet (CV), one of the earliest synthetic dyes and an ink component, is examined both in solution and on paper. Aqueous solutions of CV were exposed to UV light (365nm) and samples were taken at constant time intervals and analysed with a High Performance Liquid Chromatography-Photo Diode Array (HPLC-PDA) and Liquid Chromatography-Mass Spectroscopy (LC-MS). Demethylation products were positively identified. Also, deamination probably occurred. The oxidation at the central carbon likely generates Michlers ketone (MK) or its derivatives, but still needs confirmation. To study CV on paper, Whatman paper was immersed in CV and exposed to UV light. Before and after different irradiation periods, reflectance spectra were recorded with Fibre Optic Reflectance Spectrophotometry (FORS). A decrease in CV concentration and a change in aggregation type for CV molecules upon irradiation was observed. Colorimetric L*a*b* values before and during irradiation were also measured. Also, CV was extracted from paper before and after different irradiation periods and analysed with HPLC-PDA. Photo-fading of CV on paper produced the same products as in solution, at least within the first 100 hours of irradiation. Finally, a photo-fading of CV in the presence of MK on Whatman paper was performed. It was demonstrated that MK both accelerates CV degradation and is consumed during the reaction. The degradation pathway identified in this work is suitable for explaining the photo/fading of other dyes belonging to the triarylmethane group.

Transient EPR emission spectra of a free radical trapped in a single crystal of chloranil

Abstract The EPR spectrum of a free trapped in single crystals of chloranil changes its phase from absorption to emission when the crystal is illuminated by visible light. The time evolution of the EPR signal is discussed in terms of the interaction between the doublet species and triplet excitons produced by light excitation.

Thermoinduced Lipid Oxidation of a Culinary Oil: A Kinetic Study of the Oxidation Products by Magnetic Resonance Spectroscopies

(1)H NMR and EPR spectroscopies were employed to detect the evolution of lipid peroxidation products resulting from thermal stress in a vegetable oil. The obtained concentration profiles indicate that the secondary oxidation products (saturated and unsaturated aldehydes) may form not only via a direct degradation of primary oxidation products (hydroperoxides), as assumed in the classic kinetic models. In order to explain the observed concentration profiles, an alternate kinetic model is proposed where the aldehydes are additionally generated from hydroperoxides through an independent pathway.

Investigation of the Inner Environment of Carbon Nanotubes with a Fullerene‐Nitroxide Probe

A fulleropyrrolidine bearing a nitroxide free radical has been inserted into single-walled carbon nanotubes with the aid of supercritical CO2. Thanks to the encapsulated paramagnetic probes, it has been possible to detect and characterize the resulting peapod-like structure through electron paramagnetic resonance (EPR) spectroscopy. In particular, the analysis of spectral parameters derived from extensive EPR studies has elucidated the orientation and the residual rotational dynamics of the molecules embedded in the nanotubes. A limited anisotropic rotational freedom of the encapsulated fullerene nitroxide reveals a rather strong interaction of the probe with the surrounding nanotube walls. The interaction seems to involve the fullerene cage (as confirmed by Raman spectroscopy) and not the nitroxide moiety, whose EPR spectral characteristics, such as the isotropic hyperfine constant and the g-tensor, remain unaltered after encapsulation.

Angiotensin II-induced over-activation of p47phox in fibroblasts from hypertensives: which role in the enhanced ERK1/2 responsiveness to angiotensin II?

Background Fibroblasts are involved in the remodeling of the heart and of the vasculature associated to arterial hypertension, and an abnormal extracellular signal-regulated kinase 1/2 (ERK1/2) activation by angiotensin II (Ang II) plays a pivotal role in this process. However, the intracellular pathways leading to cell hypertrophy and hyperplasia, as well as to collagen production, are still incompletely known. Objective To investigate the role of superoxide anion (O2−) and of nicotinamide adenine dinucleotide phosphate (NAD(P)H) oxidase in Ang II-stimulated ERK1/2 over-activation in fibroblasts from hypertensive patients. Methods O2− production was measured in skin fibroblasts from hypertensives (HT, n = 11) and from normotensive controls (NT, n = 10) by electron spin resonance technique. ERK1/2 phosphorylation and p47phox NAD(P)H oxidase subunit translocation were measured by western blot. Results Ang II (1 μmol/l) induced a larger p47phox subunit translocation and increased intracellular O2− production to a larger extent in HT in comparison to NT and this effect was blocked by apocynin, an inhibitor of the NAD(P)H oxidase. Ang II increased ERK1/2 phosphorylation more in HT than in NT. The Ang II-induced ERK1/2 phosphorylation was inhibited by apocynin in a dose-dependent manner in NT, but not in HT. Conclusions The chain of cellular events leading to increased ERK1/2 responsiveness to Ang II in hypertension include an exaggerated response of p47phox, NAD(P)H oxidase and O2−, but it is partially resistant to apocynin. Therefore, NAD(P)H-dependent reactive oxygen species (ROS) production is not the only determinant of the exaggerated ERK1/2 responsiveness in fibroblasts of hypertensives (HT).