Inorganic–organic hybrid materials with zirconium oxoclusters as protective coatings on aluminium alloys

Inorganic–organic hybrid materials are attracting a strong scientific interest mainly for their outstanding inherent mechanical and thermal properties, which can be traced back to the intimate coupling of both inorganic and organic components. By carefully choosing the experimental parameters used for their synthesis, chemically and thermally stable acrylate-based hybrid material embedding the zirconium oxocluster Zr₄O₄(OMc)₁₂, where OMcCH₂C(CH₃)C(O)O, can be deposited as UV-cured films on aluminium alloys.

In particular, the molar ratios between the oxocluster and the monomer, the polymerisation time, the amount of photo-initiator and the deposition conditions, by using an home-made spray-coating equipment, were optimised in order to obtain the best performing layers in terms of transparency and hardness to coat aluminium alloy (AA1050, AA6060 and AA2024) sheets. Furthermore, it was also evaluated whether the hybrid coatings behave as barrier to corrosion.

Several coated samples were prepared and characterised. Environmental scanning electronic microscopy (ESEM) and scratch test were used to investigate the morphology of the films and to evaluate their scratch resistance, respectively. Electrochemical impedance spectroscopy (EIS) was performed in order to evaluate if the coatings actually protect the metallic substrate from corrosion.

In order to measure shear storage modulus (G′) and loss modulus (G″) of the materials used for coatings, bulk samples were also obtained by UV-curing of the precursors solution. Dynamical mechanical thermal analysis (DMTA) was performed in shear mode on cured disks of both the hybrid materials and pristine polymer for comparison. The values of T_g were read off as the temperatures of peak of loss modulus. The length and mass of all the samples were measured before and after the DMTA analysis, so that the shrinkage of the materials in that temperature range was exactly evaluated.     

Vibrational analysis of functionalized polyolefins/poly(vinylchloride) blends

Polyolefins functionalized with diethylmaleate were mixed with poly(vinylchloride) (PVC) in different compositions. Intermolecular interactions involving the carbonyl groups of the side chains of the functionalized polyolefins and methine hydrogens of PVC were investigated by means of infrared spectroscopy. The major flexibility of the ester groups attached to the backbone chains, with respect to polyesters, seems to increase the capability of such groups to interact with groups of more polar polymers, thus allowing prediction of easier miscibility, which however also depends on the starting polyolefin structure and function-alization degree.     

The effect of support morphology on the reaction of oxidative dehydrogenation of ethane to ethylene at short contact times

The oxidative dehydrogenation of ethane is carried out in short contact time reactors over Pt and LaMnO₃ based catalysts supported on a large number of different ceramic substrates (45, 60 and 80 ppi foam monoliths and 200, 400, 600, 900 and 1200 cpsi honeycomb monoliths). Experimental results, obtained under the same conditions at varying the C₂H₆/O₂ ratio, showed that the highest performance in terms of ethylene selectivity and yield is always attained on LaMnO₃ catalysts. Furthermore, the results are significantly influenced by the morphology and cell density of the support, with 45 and 60 ppi foams and 400 and 600 cpsi honeycombs giving the best performance. The experimental results are explained by means of geometrical and fluid dynamic considerations on the support, and by means of a 2D mathematical model, which clearly indicates an optimal intermediate cell density for maximising ethylene selectivity and yield.     

利用新型合成仪器解决系统级测试难题

当今世界电子元件及产品正在加速发展，在大多数商业应用中，从设计到生产的周期现已缩短为只有六个月。而且，设备的内容及拓朴结构已经从单一功能元件迁移到多功能元件，进而还会迁移到整个子系统和系统中，在迁移时通常采用单个组件方案的形式（例如，用于智能电话和iPhone之类的设备）。现在，对于多载波功率放大器（MCPA）和软件定义的无线电（SDR）而言，直接软件控制和设备配置已司空见惯。例如RFIC之类的设备只能在混合信号环境中及实时条件下操作和测试。     

Determination of the total concentration and speciation of Al(III) in tea infusions

The aluminium species in different tea infusions were investigated, by determining their stability constants and concentration. This was done for some particular samples using a simple experimental method based on the sorption of aluminium on the strongly sorbing resin Chelex 100, by a batch procedure. From the thermodynamic information obtained it is possible to calculate the concentration of the different species, and in particular that of the free metal ion, which is very important for evaluating the adsorption of aluminium on biological membranes. It was found that aluminium in the tea infusions here considered is present at high total concentration, approximately 0.1 mM, but mainly linked to strong complexes, for instance with side reaction coefficient higher than 10(5.11) at pH 3.95 in one case (tea 1). This could be the reason for the low toxicity of aluminium in tea. These strong complexes were not dissociated even in the presence of Chelex 100. In this case only a limiting value of the reaction coefficient could be evaluated. The presence of the very strong complexes was found in all the tea sample here considered. In two of the considered samples (one black and one green tea) a part of Al(III) was linked to less strong complexes, for example with a reaction coefficient 10(4.14) (tea 2, pH 4.20). The presence in the considered tea infusions of other substances able to complex aluminium was also detected, by the well known ligand titration procedure, at concentration ranging from 0.65 to 3.37 mM in three tea infusions, and at somewhat higher concentration in the case of the ready drink, which was also considered for comparison.     

The labeled maximum matching problem

Given a graph G where a label is associated with each edge, we address the problem of looking for a maximum matching of G using the minimum number of different labels, namely the labeled maximum matching problem. It is a relatively new problem whose application is related to the timetabling problem. We prove it is NP-complete and present four different mathematical formulations. Moreover, we propose an exact algorithm based on a branch-and-bound approach to solve it. We evaluate the performance of our algorithm on a wide set of instances and compare our computational times with the ones required by CPLEX to solve the proposed mathematical formulations. Test results show the effectiveness of our procedure, that hugely outperforms the solver.     

An algebraic characterization of the optimum of regularized kernel methods

The representer theorem for kernel methods states that the solution of the associated variational problem can be expressed as the linear combination of a finite number of kernel functions. However, for non-smooth loss functions, the analytic characterization of the coefficients poses nontrivial problems. Standard approaches resort to constrained optimization reformulations which, in general, lack a closed-form solution. Herein, by a proper change of variable, it is shown that, for any convex loss function, the coefficients satisfy a system of algebraic equations in a fixed-point form, which may be directly obtained from the primal formulation. The algebraic characterization is specialized to regression and classification methods and the fixed-point equations are explicitly characterized for many loss functions of practical interest. The consequences of the main result are then investigated along two directions. First, the existence of an unconstrained smooth reformulation of the original non-smooth problem is proven. Second, in the context of SURE (Stein’s Unbiased Risk Estimation), a general formula for the degrees of freedom of kernel regression methods is derived.     

The P2X7R-NLRP3 and AIM2 Inflammasome Platforms Mark the Complexity/Severity of Viral or Metabolic Liver Damage

P2X7R-NLRP3 and AIM2 inflammasomes activate caspase-1 and the release of cytokines involved in viral-related liver disease. Little is known about their role in non-alcoholic fatty liver disease (NAFLD) and non-alcoholic steato-hepatitis (NASH). We characterized the role of inflammasomes in NAFLD, NASH, and HCV. Gene expression and subcellular localization of P2X7R/P2X4R-NLRP3 and AIM2 inflammasome components were examined in histopathological preparations of 46 patients with biopsy-proven viral and metabolic liver disease using real-time PCR and immunofluorescence. P2X7R, P2X4R, and Caspase-1 are two- to five-fold more expressed in patients with NAFLD/NASH associated with chronic HCV infection than those with metabolic damage only (p ≤ 0.01 for all comparisons). The AIM2 inflammasome is 4.4 times more expressed in patients with chronic HCV infection, regardless of coexistent metabolic abnormalities (p = 0.0006). IL-2, a cytokine playing a pivotal role during chronic HCV infection, showed a similar expression in HCV and NASH patients (p = 0.77) but was virtually absent in NAFLD. The P2X7R-NLRP3 complex prevailed in infiltrating macrophages, while AIM2 was localized in Kupffer cells. Caspase-1 expression correlated with elastography-based liver fibrosis (r = 0.35, p = 0.02), whereas P2X7R, P2X4R, NRLP3, Caspase-1, and IL-2 expression correlated with circulating markers of disease severity. P2X7R and P2X4R play a major role in liver inflammation accompanying chronic HCV infection, especially when combined with metabolic damage, while AIM2 is specifically expressed in chronic viral hepatitis. We describe for the first time the hepatic expression of IL-2 in NASH, so far considered a peculiarity of HCV-related liver damage.     

Inhibitors of Mitochondrial Human Carbonic Anhydrases VA and VB as a Therapeutic Strategy against Paclitaxel-Induced Neuropathic Pain in Mice

Neuropathy development is a major dose-limiting side effect of anticancer treatments that significantly reduces patient’s quality of life. The inadequate pharmacological approaches for neuropathic pain management warrant the identification of novel therapeutic targets. Mitochondrial dysfunctions that lead to reactive oxygen species (ROS) increase, cytosolic Ca²⁺ imbalance, and lactate acidosis are implicated in neuropathic pain pathogenesis. It has been observed that in these deregulations, a pivotal role is played by the mitochondrial carbonic anhydrases (CA) VA and VB isoforms. Hence, preclinical studies should be conducted to assess the efficacy of two novel selenides bearing benzenesulfonamide moieties, named 5b and 5d, and able to inhibit CA VA and VB against paclitaxel-induced neurotoxicity in mice. Acute treatment with 5b and 5d (30–100 mg/kg, per os – p.o.) determined a dose-dependent and long-lasting anti-hyperalgesic effect in the Cold plate test. Further, repeated daily treatment for 15 days with 100 mg/kg of both compounds (starting the first day of paclitaxel injection) significantly prevented neuropathic pain development without the onset of tolerance to the anti-hyperalgesic effect. In both experiments, acetazolamide (AAZ, 100 mg/kg, p.o.) used as the reference drug was partially active. Moreover, ex vivo analysis demonstrated the efficacy of 5b and 5d repeated treatments in reducing the maladaptive plasticity that occurs to glia cells in the lumbar portion of the spinal cord and in improving mitochondrial functions in the brain and spinal cord that were strongly impaired by paclitaxel-repeated treatment. In this regard, 5b and 5d ameliorated the metabolic activity, as observed by the increase in citrate synthase activity, and preserved an optimal mitochondrial membrane potential (ΔΨ) value, which appeared depolarized in brains from paclitaxel-treated animals. In conclusion, 5b and 5d have therapeutic and protective effects against paclitaxel-induced neuropathy without tolerance development. Moreover, 5b and 5d reduced glial cell activation and mitochondrial dysfunction in the central nervous system, being a promising candidate for the management of neuropathic pain and neurotoxicity evoked by chemotherapeutic drugs.