Negatively Charged Metallacarborane Redox Couples with Both Members Stable to Air

The metallacarborane [3,3′‐Co(1,2‐closo‐C₂B₉H₁₁)₂]^? has been synthesized. This species allows the formation of redox couples in which both partners are negatively charged. The E_1/2 potential can be tuned by adjusting the nature and number of substituents on B and C. The octaiodinated species [3,3′‐Co(1,2‐closo‐C₂B₉H₇I₄)₂]^? is the most favorable, as it is isolatable and stable in air. A DFT study on stability and redox potentials of complexes has been performed.     

The Cytotoxic Effect of α-Synuclein Aggregates

Parkinson's disease is a neurodegenerative disorder involving a functional protein, α-synuclein, whose primary function is related to vesicle trafficking. However, α-synuclein is prone to form aggregates, and these inclusions, known as Lewy bodies, are the hallmark of Parkinson's disease. α-synuclein can alter its conformation and acquire aggregating capacity, forming aggregates containing β-sheets. This protein's pathogenic importance is based on its ability to form oligomers that impair synaptic transmission and neuronal function by increasing membrane permeability and altering homeostasis, generating a deleterious effect over cells. First, we establish that oligomers interfere with the mechanical properties of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) membrane, as demonstrated by nanoindentation curves. In contrast, nanoindentation revealed that the α-synuclein monomer's presence leads to a much more resistant lipid bilayer. Moreover, the oligomers’ interaction with cell membranes can promote lactate dehydrogenase (LDH) release, suggesting the activation of cytotoxic events.     

On the Convenience to Form Coalitions or Partnerships in Simple Games

A partnership in a cooperative game is a coalition that possesses an internal structure and, simultaneously, behaves as an individual member. Forming partnerships leads to a modification of the original game which differs from the quotient game that arises when one or more coalitions are actually formed. In this paper, the Shapley value is used to discuss the convenience to form either coalitions or partnerships. To this end, the difference between the additive Shapley value of the partnership in the partnership game and the Shapley alliance value of the coalition, and also between the corresponding value of the internal and external players, are analysed. Simple games are especially considered. Research partially supported by Grant BFM 2003-01314 of the Science and Technology Spanish Ministry and the European Regional Development Fund.     

Automorphisms and blocking in simple games

Different (proper as well as improper) simple games may share any nonseparating blocking family. An interesting question is whether all such proper games on one hand, and all improper ones on the other, are isomorphic. The answer is given here and the automorphisms of the blocking family help us to understand the structure and links of all such games.     

Summing the derivative expansion of the effective action

The derivative expansion of the effective action is a perturbative development in derivatives of the fields. The expansion breaks down when some of the derivatives are too large. We show how to sum exactly the first and second derivatives and treat perturbatively derivatives higher than second.     

Monte Carlo Simulation of Electron Transport and X-Ray Generation. II. Radiative Processes and Examples in Electron Probe Microanalysis

Theoretical models for Monte Carlo simulation of radiative processes, i.e. bremsstrahlung and characteristic x-ray emission, are presented. Possible strategies for simulating electron transport are briefly described. For mechanisms involving energy loss and angular deflections, difficulties for strict implementation of accurate numerical differential cross sections still remain due to the strong correlations between these variables. Practical solutions for the case of inelastic collisions and bremsstrahlung emission are described. Comparisons of simulation results with experimental data for several problems of interest in electron probe microanalysis are presented.     

Electrochemistry nanometric patterning of MOF particles: Anisotropic metal electrodeposition in Cu/MOF

Electrodeposition of copper from Cu/MOF immersed into acetate buffer produces a quasi-periodic series of 10–20 nm sized laminae sandwiched within the pristine MOF lattice as monitored by voltammetry of microparticles/atomic force microscopy. This anisotropic patterning can be qualitatively described in terms of a highly orientation-dependent diffusion of electrons and charge-balancing electrolyte counterions in the MOF network.     

Gold ultra-microelectrode arrays: application to the steady-state voltammetry of hydroxide ion in aqueous solution.

Gold ultra-microelectrode arrays are used to explore the electrochemical oxidation of hydroxide ions and are shown to be analytical useful. Two types of ultra-microelectrode arrays are used; the first consist of 256 individual electrodes of 5 microm in radius, 170 of which are electrochemically active in a cubic arrangement which are separated from their nearest neighbour by a distance of 100 microm. The second array compromises 2597 electrodes of 2.5 microm in radius and of which 1550 of which are electrochemically active in a hexagonal arrangement separated by the nearest neighbour by 55 microm. Well defined voltammetric waves are found with peak currents proportional to the concentration of hydroxide ions in the range 50 microM to 1 mM. Detection limits of 20 microM using the 170 ultra-microelectrode and 10 microM with the 1550 ultra-microelectrode array are shown to be possible but with a higher sensitivity of 4 mA M(-1) observed using the 1550 ultra-microelectrode array compared to 1.2 mA M(-1) with the 170 ultra-microelectrode array.