SFG and DFG investigation of Au(111), Au(210), polycrystalline Au,Au–Cu and Au–Ag–Cu electrodes in contact with aqueous solutions containing KCN and 4-cyanopyridine

We report on potential-dependent in situ SFG and DFG spectroscopy carried out at Au(111), Au(210), polycrystalline Au, Au–Cu and Au–Ag–Cu electrodes in contact with aqueous solutions containing CN⁻ and 4-cyanopyridine (4CP). Spectroelectrochemical work was complemented by cyclic voltammetry. The chief stress has been placed on systematising and quantifying the interaction between 4CP and CN⁻ and the attending effects on the vibrational and electronic structures of the interface. The voltammetric behaviour of the investigated electrodes, modified by the addition of 4CP to the CN⁻ electrolyte, denote changes in the CN⁻ adsorption characteristics and effects of the adsorbed CN⁻ layer on the electrodic reactivity of 4CP. The differences among the investigated electrodes can be explained in terms of their respective degrees of atomic packing or with alloying effects on the stability of adsorbed CN⁻. The potential-dependent spectra have been analysed quantitatively with a model for the second order non linear susceptibility accounting for vibrational and electronic effects. The spectral changes induced by addition of 4CP denote interaction of the aromatic with the electrode through the CN⁻ monolayer. The non-resonant contribution yields information on the effects of 4CP on the fine structure of the bound electron density of states.     

Reaction kinetics modeling and thermal properties of epoxy–amines as measured by modulated‐temperature DSC. II. Network‐forming DGEBA + MDA

Reaction‐induced vitrification takes place in the network‐forming epoxy–amine system diglycidyl ether of bisphenol A (DGEBA) + methylenedianiline (MDA) when the glass‐transition temperature (T_g) rises above the cure temperature (T_cure). This chemorheological transition results in diffusion‐controlled reaction and can be followed simultaneously with the reaction rate in modulated‐temperature DSC (MTDSC). To predict the effect of T_cure and the NH/epoxy molar mixing ratio (r) on the reaction rate in chemically controlled conditions, a mechanistic approach was used based on the nonreversing heat flow and heat capacity MTDSC signals, in which the reaction steps of primary (E_1OH = 44 kJ mol^?1) and secondary amine (E_2OH = 48 kJ mol^?1) with the epoxy–hydroxyl complex predominating. The diffusion factor DF as defined by the Rabinowitch approach expresses whether the chemical reaction rate or the diffusion rate determines the overall reaction rate. A model based on the free volume theory together with an Arrhenius temperature dependency was used to calculate the diffusion rate constant in DF as a function of conversion (x) and T_cure. The relation between x, r, and T_g, needed in this model, can be predicted with the Couchman equation. An experimental approximation for DF is the mobility factor DF* obtained from the heat capacity signal at a modulation frequency of 1/60 Hz, normalized for the effect of the reaction heat capacity in the liquid state and the change in C_p in the glassy region with x and T_cure. In this way, an optimized set of diffusion parameters was obtained that, together with the optimized kinetic parameters set, can predict the reaction rate for different cure schedules and for stoichiometric and off‐stoichiometric mixtures. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2814–2833, 2004     

On the observation of inductive high-frequency impedance behaviour during the electrodeposition of Au—Sn alloys

Inductive high-frequency impedance behaviour is often observed in metal electrodeposition systems. This behaviour is typically attributed to equipment limitations or non-idealities in the cell set-up and electrical connections. Such instrumental artefacts would nevertheless be relevant to a frequency range which is expected to be well above that in which inductive behaviour is in fact observed (down to a few tens of Hz). In this paper some results on an acidic Au—Sn electrodeposition system are reported. Electrochemical impedance and potentiostatic transients were measured. These results suggest that the high-frequency inductive behaviour may be related to metal nucleation processes. A correlation is proposed between the pseudo-inductive potentiostatic nucleation transients and the pseudo-inductive behaviour of the impedance spectra.     

Robust procedures in multiple regression: P-subsets and a computational proposal

A number of robust and diagnostic techniques for the linear regression are in terms of p-dimensional subsets of the original sample. In a sample of size n this leads to consider ⁿ C _p subsets. To reduce the computational burden, a limited number of subsets can be selected by means of a sub-sampling scheme. In this paper we suggest and discuss the use of a Balanced Incomplete Block design plan.     

CD73-Adenosinergic Axis Mediates the Protective Effect of Extracellular Vesicles Derived from Mesenchymal Stromal Cells on Ischemic Renal Damage in a Rat Model of Donation after Circulatory Death

We propose a new organ-conditioning strategy based on mesenchymal stromal cell (MSCs)/extracellular vesicle (EVs) delivery during hypothermic perfusion. MSCs/EVs marker CD73 is present on renal proximal tubular cells, and it protects against renal ischemia-reperfusion injury by converting adenosine monophosphate into adenosine (ADO). In this study, after checking if CD73-silenced EVs (EVsi) would impact in vitro tubular-cell proliferation, we perfused kidneys of a rat model of donation after circulatory death, with Belzer solution (BS) alone, BS supplemented with MSCs, EVs, or EVsi. The ADO and ATP levels were measured in the effluents and tissues. Global renal ischemic damage score (GRS), and tubular cell proliferation index (IPT) were evaluated in the tissue. EVsi did not induce cell proliferation in vitro. Ex vivo kidneys perfused with BS or BS + EVsi showed the worst GRS and higher effluent ADO levels than the MSC- and EV-perfused kidneys. In the EV-perfused kidneys, the tissue and effluent ATP levels and IPT were the highest, but not if CD73 was silenced. Tissue ATP content was positively correlated with tissue ADO content and negatively correlated with effluent ADO level in all groups. In conclusion, kidney conditioning with EVs protects against ischemic damage by activating the CD73/ADO system.     

Novel ferrofluids coated with a renewable material obtained from cashew nut shell liquid

In this work, we present the synthesis and characterization of a new surfactant molecule obtained from a byproduct of the cashew nut processing (diphosphorylated cardol, DPC). It is herein used to overcoat magnetic nanoparticles showing spinel structures in order to create new ferrofluids. The nanoparticle structure and magnetic properties have been deeply investigated. DPC-functionalized Fe₃O₄ and NiFe₂O₄ samples exhibit higher magnetic saturation than DPC–CoFe₂O₄. These new ferrofluids reveal appealing as possible nanoparticle stabilizing molecules, magnetic resonance imaging agents, storage systems or in any material science field that requires the employment of biocompatible magnetic stable fluids.     

An Innovative Science Gateway for the Cherenkov Telescope Array

The Cherenkov Telescope Array (CTA) is currently building the next generation, ground-based, very high-energy gamma-ray instrumentation. CTA is expected to collect very large datasets (in the order of petabytes) which will have to be stored, managed and processed. This paper presents a graphical user interface built inside a science gateway aiming at providing CTA-users with a common working framework. The gateway is WS-PGRADE/gUSE workflow-oriented and is equipped with a flexible SSO (based on SAML) to control user access for authentication and authorization. An interactive desktop environment is provided, called Astronomical & Physics Cloud Interactive Desktop (ACID). Users are able to exploit the graphical interface as provided natively by the tools included in ACID. A cloud data service shares and synchronizes data files and output results between the user desktop and the science gateway. Our solution is a first attempt towards an ecosystem of new technologies with a high level of flexibility to suit present and future requirements of the CTA community.     

The proton iron-sulfur cluster environment of the [FeFe]-hydrogenase maturation protein HydF from Thermotoga neapolitana

[FeFe]-hydrogenases contain a complex [4Fe–4S]-2Fe cluster (H-cluster) and are able to efficiently reduce protons to H₂. Due to their potential exploitation for renewable energy production biotechnologies, significant efforts have been put into understanding the mechanisms driving the H-cluster assembly, which involves three conserved proteins. Among them, HydF works as scaffold upon which the H-cluster precursor is synthesized and carrier to deliver it to the hydrogenase, resulting in its activation. A FeS cluster binding sequence (CxHx₄₆-₅₃HCxxC) is conserved in all HydF proteins and should in principle provide four ligands to coordinate the Fe atom. However, we found that alternative metal coordination may exist in different HydF proteins and that only the three cysteines are strictly required, whereas the fourth ligand may vary and is, in any case, readily exchangeable. In this work we analyzed by EPR/HYSCORE the FeS cluster proton environment of HydF from Thermotoga neapolitana to determine the possible role of surrounding residues in the non-cysteinyl iron ligation of the protein.     

Complexity analysis of blast-induced vibrations in underground mining:A case study

Blasting in geological bodies is an industrial process acting in an environment characterized by high uncertainties (natural joints,faults,voids,abrupt structural changes),which are transposed into the...     

Electrochemical behaviour of titanium in fluoride-containing saliva

The effect of fluoride on the electrochemical behaviour of titanium was studied. Open circuit potentials, breakdown potentials (E _b) and potentiostatic transient currents were measured in synthetic salivas of different compositions. Optical and scanning electron microscopic observations were also made. Results show that the growth rate of Ti oxide layer is affected by fluoride anions and tensile stresses are developed. The OCP/time relationship of Ti immersed in salivas A and B obeys a logarithmic law which depends on the saliva composition. The E _b value is influenced by the thickness of the oxide layer, by the composition of the saliva (including fluoride concentration), and by the technique utilised for its evaluation. Thus, results reported in the literature, which seem to be contradictory, could be explained taking into account the experimental conditions assayed. A careful control of the titanium-containing dental materials should be made after long treatments with fluoride-containing prophylactic products or when fluoride-releasing restorative materials are present in the vicinity.