Mechanistic Insight into the Catechol Oxidase Activity by a Biomimetic Dinuclear Copper Complex

The biomimetic catalytic oxidation of 3,5-ditert- butylcatechol by the dicopper(II) complex of the ligand a,a¢-bis{bis[1-(1¢-methyl-2¢-benzimidazolyl) methyl]amino}-m-xylene in the presence of dioxygen has been investigated as a function of temperature and pH in a mixed aqueous/organic solvent. The catalytic cycle occurs in two steps, the first step being faster than the second step. In the first step, one molecule of catechol is oxidized by the dicopper(II) complex, and the copper(II) centers are reduced. From the pH dependence, it is deduced that the active species of the process is the monohydroxo form of the dinuclear complex. In the second step, the second molecule of catechol is oxidized by the dicopper(I)-dioxygen complex formed upon oxygenation of the reduced complex. In both cases, catechol oxidation is an inner-sphere electron transfer process involving binding of the catechol to the active species. The binary catechol-dicopper(II) complex formed in the first step could be characterized at very low temperature (90 C), where substrate oxidation is blocked. On the contrary, the ternary complex of dicopper( I)-O2-catechol relevant to the second step does not accumulate in solution and could not be characterized, even at low temperature. The investigation of the biphasic kinetics of the catalytic reaction over a range of temperatures allowed the thermodynamic (DH and DS) and activation parameters (DH „ and DS „ ) connected with the key steps of the catecholase process to be obtained

TRADES: A new software to derive orbital parameters from observed transit times and radial velocities. Revisiting Kepler-11 and Kepler-9

Aims. With the purpose of determining the orbital parameters of exoplanetary systems from observational data, we have developed a software, named TRADES (TRAnsits and Dynamics of Exoplanetary Systems), to simultaneously fit observed radial velocities and transit times data. Methods. We implemented a dynamical simulator for N-body systems, which also fits the available data during the orbital integration and determines the best combination of the orbital parameters using grid search, $\chi^2$ minimization, genetic algorithms, particle swarm optimization, and bootstrap analysis. Results. To validate TRADES, we tested the code on a synthetic three-body system and on two real systems discovered by the Kepler mission: Kepler-9 and Kepler-11. These systems are good benchmarks to test multiple exoplanet systems showing transit time variations (TTVs) due to the gravitational interaction among planets. We have found that orbital parameters of Kepler-11 planets agree well with the values proposed in the discovery paper and with a a recent work from the same authors. We analyzed the first three quarters of Kepler-9 system and found parameters in partial agreement with discovery paper. Analyzing transit times (T0s) covering 12 quarters of Kepler data, that we have found a new best-fit solution. This solution outputs masses that are about 55% of the values proposed in the discovery paper; this leads to a reduced semi-amplitude of the radial velocities of about 12.80 m/s.Comment: 14 pages, 13 figures, 6 tables; accepted for publication in Astronomy & Astrophysics, and corrected by the Language Edito

Development and Techno-Economic Analysis of an Advanced Recycling Process for Photovoltaic Panels Enabling Polymer Separation and Recovery of Ag and Si

Photovoltaic panels were included in EU Directive as WEEE (Wastes of Electric and Electronic Equipment) requiring the implementation of dedicated collection schemes and end-of-life treatment ensuring targets in terms of recycling rate (80%) and recovery rate (85%). Photovoltaic panels are mainly made up of high-quality solar glass (70–90%), but also metals are present in the frames (Al), the cell (Si), and metallic contacts (Cu and Ag). According to the panel composition, about $72 per 100 kg of panels can be recovered by entirely recycling the panel metal content. The PhotoLife process for the treatment of end-of-life photovoltaic panels was demonstrated at pilot scale to recycle high value glass, Al and Cu scraps. A process upgrade is here reported allowing for polymer separation and Ag and Si recycling. By this advanced PhotoLife process, 82% recycling rate, 94% recovery rate, and 75% recoverable value were attained. Simulations demonstrated the economic feasibility of the process at processing capacity of 30,000 metric ton/y of end-of-life photovoltaic panels

Synthetic Crysotile Nano-Crystals as a Reference Standard to Investigate Surface-Induce Serum Albumin Structural Modifications

Geoinspired synthetic chrysotile, which represents an ideal asbestos reference standard, has been utilized to investigate homomolecular exchange of bovine serum albumin (BSA), the major plasma protein, between the adsorbed and dissolved state at the interface between asbestos fibers and biological medium. FTIR spectroscopy has been used to quantify BSA structural modifications due to surface adhesion on chrysotile fibers as a function of the surface coating extent. Circular dichroism spectroscopy has been used to investigate the adsorption/desorption equilibrium through analysis of the BSA structural perturbations after protein desorption from chrysotile surface. Data results show clearly that in the solid state BSA modifications are driven by surface interaction with the substrate, following a bimodal adsorption evidenced by two different binding constants. On the other hand, BSA desorbed in solution is able to rearrange, in the lack of substrate, although keeping irreversible modifications with respect to the native species. The lack of regaining its native structure certainly affects albumin interaction with biological environment. The present investigation on the stoichiometric synthetic geoinspired chrysotile nanocrystals is the first approach toward a deeper attempt to use standard synthetic chrysotile reference samples in mimicking the behavior of asbestos fibers and allows to better understand their interaction with a biological environment

A PSF-based approach to Kepler/K2data – III. Search for exoplanets and variable stars within the open cluster M 67 (NGC 2682)

In the third paper of this series we continue the exploitation of Kepler/K2 data in dense stellar fields using our PSF-based method. This work is focused on a ~720-arcmin^2 region centred on the Solar-metallicity and Solar-age open cluster M 67. We extracted light curves for all detectable sources in the Kepler channels 13 and 14, adopting our technique based on the usage of a high-angular-resolution input catalogue and target-neighbour subtraction. We detrended light curves for systematic errors, and searched for variables and exoplanets using several tools. We found 451 variables, of which 299 are new detection. Three planetary candidates were detected by our pipeline in this field. Raw and detrended light curves, catalogues, and K2 stacked images used in this work will be released to the community.Comment: 14 pages, 9 figures (1 at low resolution), 3 tables. Accepted for publication in MNRAS on August 24, 2016. Electronic materials are available at http://groups.dfa.unipd.it/ESPG/Kepler-K2.htm

Inhibition of heparanase protects against chronic kidney dysfunction following ischemia/reperfusion injury

Renal ischemia/reperfusion (I/R) injury occurs in patients undergoing renal transplantation and with acute kidney injury and is responsible for the development of chronic allograft dysfunction as characterized by parenchymal alteration and fibrosis. Heparanase (HPSE), an endoglycosidase that regulates EMT and macrophage polarization, is an active player in the biological response triggered by ischemia/reperfusion (I/R) injury. I/R was induced in vivo by clamping left renal artery for 30 min in wt C57BL/6J mice. Animals were daily treated and untreated with Roneparstat (an inhibitor of HPSE) and sacrificed after 8 weeks. HPSE, fibrosis, EMT-markers, inflammation and oxidative stress were evaluated by biomolecular and histological methodologies together with the evaluation of renal histology and measurement of renal function parameters. 8 weeks after I/R HPSE was upregulated both in renal parenchyma and plasma and tissue specimens showed clear evidence of renal injury and fibrosis. The inhibition of HPSE with Roneparstat-restored histology and fibrosis level comparable with that of control. I/R-injured mice showed a significant increase of EMT, inflammation and oxidative stress markers but they were significantly reduced by treatment with Roneparstat. Finally, the inhibition of HPSE in vivo almost restored renal function as measured by BUN, plasma creatinine and albuminuria. The present study points out that HPSE is actively involved in the mechanisms that regulate the development of renal fibrosis arising in the transplanted organ as a consequence of ischemia/reperfusion damage. HPSE inhibition would therefore constitute a new pharmacological strategy to reduce acute kidney injury and to prevent the chronic pro-fibrotic damage induced by I/R

Sex steroids, carcinogenesis, and cancer progression

The relationship between sex steroids and cancer has been studied for more than a century. Using an original intact cell analysis, we investigated sex steroid metabolism in a panel of human cancer cell lines, either hormone responsive or unresponsive, originating from human breast, endometrium, and prostate. We found that highly divergent patterns of steroid metabolism exist and that the catalytic preference (predominantly reductive or oxidative) is strictly associated with the steroid receptor status of cells. We explored intra-tissue concentrations and profiles of estrogens in a set of human breast tumors as compared to normal mammary tissues, also in relation to their estrogen receptor status. In particular, we showed that, with hydroxyestrogens representing the majority of all tissue estrogens, concentrations of individual metabolites, as well as their ratios, significantly differ when comparing normal tissue with cancer tissues or when they are related to the overall survival of cancer patients. © 2004 New York Academy of Sciences

Management of Low-Risk Thyroid Cancers: Is Active Surveillance a Valid Option? A Systematic Review of the Literature.

Thyroid cancer is the most common endocrine malignancy, representing 2.9% of all new cancers in the United States. It has an excellent prognosis, with a five-year relative survival rate of 98.3%.Differentiated Thyroid Carcinomas (DTCs) are the most diagnosed thyroid tumors and are characterized by a slow growth rate and indolent course. For years, the only approach to treatment was thyroidectomy. Active surveillance (AS) has recently emerged as an alternative approach; it involves regular observation aimed at recognizing the minority of patients who will clinically progress and would likely benefit from rescue surgery. To better clarify the indications for active surveillance for low-risk thyroid cancers, we reviewed the current management of low-risk DTCs with a systematic search performed according to a PRISMA flowchart in electronic databases (PubMed, Web of Science, Scopus, and EMBASE) for studies published before May 2021. Fourteen publications were included for final analysis, with a total number of 4830 patients under AS. A total of 451/4830 (9.4%) patients experienced an increase in maximum diameter by >3 mm; 609/4830 (12.6%) patients underwent delayed surgery after AS; metastatic spread to cervical lymph nodes was present in 88/4213 (2.1%) patients; 4/3589 (0.1%) patients had metastatic disease outside of cervical lymph nodes. Finally, no subject had a documented mortality due to thyroid cancer during AS. Currently, the American Thyroid Association guidelines do not support AS as the first-line treatment in patients with PMC; however, they consider AS to be an effective alternative, particularly in patients with high surgical risk or poor life expectancy due to comorbid conditions. Thus, AS could be an alternative to immediate surgery for patients with very-low-risk tumors showing no cytologic evidence of aggressive disease, for high-risk surgical candidates, for those with concurrent comorbidities requiring urgent intervention, and for patients with a relatively short life expectancy