Diffusion regimes at nanoelectrode ensembles in different ionic liquids

The electrochemical and diffusion behaviour of different redox probes in different ionic liquids is studied at gold nanoelectrode ensembles (NEEs) in comparison with millimetre sized gold (Au-macro) and glassy carbon (GC) disk electrodes. The redox probes are neutral ferrocene (Fc), the ferrocenylmethyltrimetylammonium cation (FA⁺) and the ferrocenylmonocarboxylate anion (FcCOO⁻). The ILs are the dicyanamide, [N(CN)₂] or bis(trifluoromethylsulfonyl)amide), [N(Tf)₂] salts of the following cations: 1-butyl-3-methylimidazolium, [BMIm], 1-butyl-3-methylpyrrolidonium, [BMPy], or tris(n-hexyl)tetradecylphosphonium [P_14,666]. These ILs are characterized by different viscosities, ranging from 32 to 277 cP. The cyclic voltammetric behaviour of the redox probes is reversible and diffusion controlled at GC electrodes. Diffusion coefficients (D) calculated by the Randles-Sevcik equation scales inversely with the IL viscosity, ranging from 2 × 10⁻⁸ to 3 × 10⁻⁷ cm² s⁻¹. Ionic solutes, namely FA⁺ and FcCOO⁻, present slightly lower D values than neutral Fc. At the Au-macro the electrochemical behaviour of the redox probes is diffusion controlled in the ILs containing the [N(Tf)₂] anion, while it involves relevant adsorption processes in the [N(CN)₂] containing electrolyte. For this reason the diffusion at gold NEEs is studied only in the former ILs.The CVs of the redox probes at the NEEs are peak shaped at low scan rate (v), while they are sigmoidally shaped at high v, but with some shift between forward and backward patterns. This is indicative of the occurrence of a total overlap (TO) diffusion condition when v is low which becomes a mixed diffusion layers (MDL) regime, with only a partial overlapping of individual diffusion layers, at high v values. In the most viscous IL, namely [P_14,666] [N(Tf)₂], at v higher than 0.8 V s⁻¹, a plateau current independent on the scan rate is achieved, indicating the tendency to reach the pure radial regime in this IL. The v values at which the transition between TO and MDL is observed scales directly with D and inversely with the IL viscosity. This behaviour is interpreted on the basis of the dependence of individual diffusion layers at each nanoelectrode on redox probe/IL interaction which fits with existing theoretical models very recently developed for nanoelectrode arrays.     

A simple model for the photocurrent density of a graded band gap CIGS thin film solar cell

A simple model for the photocurrent density of a linearly graded band gap Cu(In,Ga)Se₂ solar cell is presented. Both generation and recombination mechanisms in the space charge region and absorber region of the cell are considered. The carrier collection function and effective absorption coefficient are introduced in the calculations to obtain a more realistic model. The results show that photocurrent density of the graded band-gap solar cell is higher than that with a constant averaged band gap. There is an optimum for grading strength or band gap widening of the absorber region. Recombination current reduces the photocurrent density with a lower reduction in the absorber material than in the depletion region. For longer diffusion lengths (or greater values of carrier collection factor), a higher photocurrent density is obtained except where collection probability is already unity everywhere in the absorber.     

Toward a better understanding of multifunctional cement-based materials: The impact of graphite nanoplatelets (GNPs)

The impact of graphite nanoplatelets (GNPs) on the physical and mechanical properties of cementitious nanocomposites was investigated. A market-available premixed mortar was modified with 0.01% by weight of cement of commercial GNPs characterized by two distinctively different aspect ratios.The rheological behavior of the GNP-modified fresh admixtures was thoroughly evaluated. Hardened cementitious nanocomposites were investigated in terms of density, microstructure (Scanning Electron Microscopy, SEM and micro–Computed Tomography, μ-CT), mechanical properties (three-point bending and compression tests), and physical properties (electrochemical impedance spectroscopy, EIS and thermal conductivity measurements). At 28 days, all GNP-modified mortars showed about 12% increased density. Mortars reinforced with high aspect ratio GNPs exhibited the highest compressive and flexural strength: about 14% and 4% improvements compared to control sample, respectively. Conversely, low aspect ratio GNPs led to cementitious nanocomposites characterized by 36% decreased electrical resistivity combined with 60% increased thermal conductivity with respect to the control sample.     

Amyloid-Beta Induces Different Expression Pattern of Tissue Transglutaminase and Its Isoforms on Olfactory Ensheathing Cells: Modulatory Effect of Indicaxanthin

Herein, we assessed the effect of full native peptide of amyloid-beta (Aβ) (1-42) and its fragments (25-35 and 35-25) on tissue transglutaminase (TG2) and its isoforms (TG2-Long and TG2-Short) expression levels on olfactory ensheathing cells (OECs). Vimentin and glial fibrillary acid protein (GFAP) were also studied. The effect of the pre-treatment with indicaxanthin from Opuntia ficus-indica fruit on TG2 expression levels and its isoforms, cell viability, total reactive oxygen species (ROS), superoxide anion (O₂⁻), and apoptotic pathway activation was assessed. The levels of Nestin and cyclin D1 were also evaluated. Our findings highlight that OECs exposure to Aβ(1-42) and its fragments induced an increase in TG2 expression levels and a different expression pattern of its isoforms. Indicaxanthin pre-treatment reduced TG2 overexpression, modulating the expression of TG2 isoforms. It reduced total ROS and O₂⁻ production, GFAP and Vimentin levels, inhibiting apoptotic pathway activation. It also induced an increase in the Nestin and cyclin D1 expression levels. Our data demonstrated that indicaxanthin pre-treatment stimulated OECs self-renewal through the reparative activity played by TG2. They also suggest that Aβ might modify TG2 conformation in OECs and that indicaxanthin pre-treatment might modulate TG2 conformation, stimulating neural regeneration in Alzheimer’s disease.     

Exploring Molecular Contacts of MUC1 at CIN85 Binding Interface to Address Future Drug Design Efforts

The modulation of protein-protein interactions (PPIs) by small molecules represents a valuable strategy for pharmacological intervention in several human diseases. In this context, computer-aided drug discovery techniques offer useful resources to predict the network of interactions governing the recognition process between protein partners, thus furnishing relevant information for the design of novel PPI modulators. In this work, we focused our attention on the MUC1-CIN85 complex as a crucial PPI controlling cancer progression and metastasis. MUC1 is a transmembrane glycoprotein whose extracellular domain contains a variable number of tandem repeats (VNTRs) regions that are highly glycosylated in normal cells and under-glycosylated in cancer. The hypo-glycosylation fosters the exposure of the backbone to new interactions with other proteins, such as CIN85, that alter the intracellular signalling in tumour cells. Herein, different computational approaches were combined to investigate the molecular recognition pattern of MUC1-CIN85 PPI thus unveiling new structural information useful for the design of MUC1-CIN85 PPI inhibitors as potential anti-metastatic agents.     

Rapid and Simultaneous Analysis of Xanthines and Polyphenols as Bitter Taste Markers in Bakery Products by FT-NIR Spectroscopy

The food industry has a direct interest into bitter-tasting substances either for the identification of negative off-flavors or for the monitoring of a desired organoleptic quality. A rapid technique, based on Fourier transform-near infrared (FT-NIR) spectroscopy and able to detect taste molecular markers in bakery commodities, was developed, focusing the attention on biscuits category. Xanthines (caffeine, theobromine, and theophylline) and polyphenols (catechins and epicathechins), considered as mainly responsible for the bitter-taste of coffee\cocoa\chocolate based products, were firstly checked using a confirmatory liquid chromatography (LC)-ESI\mass spectrometry (MS)-MS procedure after hot methanol–water extraction. Correspondent data were used for the calibration of the FT-NIR through PLS regression. Values of the standard errors of prediction (lower than 10 %) were comparable to the values of the standard errors of cross-validation. Coefficients of determination indicated a good predictive power in the calibration model (R ² xanthines?=?0.97, R ² polyphenols?=?0.96) and a satisfying discriminating power among different contents in the validation models (R ² xanthines?=?0.96, R ² polyphenols?=?0.96). A testing phase on the generated model was executed by a comparison of LC-MS and sensory panel data with FT-NIR responses recorded on unknown biscuits: differences between found and predicted levels were generally below 5 % and the best predictability was achievable in chocolate-based biscuits. This methodology is able to work directly on solid products, has the potential to be expanded on other categories of gustative molecular markers (like sugars) and can be conceived as applicable for a routine control of a standardized bitter taste quality in a real industrial production.     

Stubborn Sets for Real-Time Petri Nets

The stubborn-set method attempts to reduce the number of states that must be explicitly enumerated during reachability analysis of a concurrent system, while preserving crucial concurrency properties in the reduced state space. Here we extend the method to the analysis of certain timed models. We also prove that timing properties of interest, such as minimum and maximum delays between events, are preserved in the reduced model. Finally, we report on some experimental results that we have obtained with our extension. These results show that real-time stubborn sets can often provide significant reductions in state space size.     

Synchronization Algebras with Mobility for Graph Transformations

We propose a generalization of synchronization algebras that allows to deal with mobility and local resource handling. We show how it can be used to model communication primitives for distributed and mobile computations, such as the ones used in the global computing area. We propose a graph transformation formalism in the Synchronized Hyperedge Replacement approach which is parametric w.r.t. the synchronization algebra and thus allows to model complex systems based on the chosen communication primitives. We thus unify different models described in the literature and we allow to easily define new ones. We present various examples and a case study on Fusion Calculus, showing how different semantics for it can be derived using different synchronization algebras.