Cationic Dye Modified Sawdust as Electrode Modifier for Electrochemical Detection of Anions

Because of its chemical properties, sawdust displays poor anionic exchange capacity. Here we demonstrate that sawdust modification with methylene blue (MB) dye represents an interesting and facile alternative to render this natural biomaterial capable to accumulate anionic species. MB adsorption onto sawdust was monitored by cyclic voltammetry and experimental parameters carefully optimized. Under the ideal experimental conditions (composition of accumulation and desorption solution, accumulation and desorption time and the nature of the electrolytic solution), the adsorbed MB showed poor mobility, which results in the absence of the characteristic electrochemical signal of MB. The ability of the material to accumulate anionic species was thus evaluated using Fe(CN)₆^3? as a model anions. The slow Fe(CN)₆^3?/4? system recorded onto the electrode modified by pristine sawdust (P/SFE) become fast and reversible after immobilization of MB onto P/SFE (MB/SFE). Electrochemical impedance spectroscopy confirms this result through the spectacular decrease of charge transfer resistance after MB adsorption (from 83 kΩ on P/SFE to 637 Ω on MB/SFE). MB/SFE was applied to the electroanalysis of nitrites and a sensitivity of 7.4 μA mM^?1 was obtained. Although this sensitivity was less important compared to that obtained on glassy carbon electrode (9.4 μA mM^?1), the dye modified electrode displays by far the best reproducibility even at higher nitrite concentration.     

Exploring weight-dependent density-functional approximations for ensembles in the Hubbard dimer

Gross–Oliveira–Kohn density-functional theory (GOK-DFT) is an extension of DFT to excited states where the basic variable is the ensemble density, i.e. the weighted sum of ground- and excited-state densities. The ensemble energy (i.e. the weighted sum of ground- and excited-state energies) can be obtained variationally as a functional of the ensemble density. Like in DFT, the key ingredient to model in GOK-DFT is the exchange-correlation functional. Developing density-functional approximations (DFAs) for ensembles is a complicated task as both density and weight dependencies should in principle be reproduced. In a recent paper [K. Deur et al., Phys. Rev. B 95, 035120 (2017)], the authors applied exact GOK-DFT to the simple but nontrivial Hubbard dimer in order to investigate (numerically) the importance of weight dependence in the calculation of excitation energies. In this work, we derive analytical DFAs for various density and correlation regimes by means of a Legendre–Fenchel transform formalism. Both functional and density driven errors are evaluated for each DFA. Interestingly, when the ensemble exact-exchange-only functional is used, these errors can be large, in particular if the dimer is symmetric, but they cancel each other so that the excitation energies obtained by linear interpolation are always accurate, even in the strongly correlated regime.     

The sub-ODE method for finding exact travelling wave solutions of generalized nonlinear Camassa-Holm, and generalized nonlinear Schrödinger equations

With the aid of the ordinary differential equation (ODE) involving an arbitrary positive power of dependent variable proposed by Li and Wang and an indirect F-function method very close to the F-expansion method, we solve the generalized Camassa-Holm equation with fully nonlinear dispersion and fully nonlinear convection C(l,n,p) and the generalized nonlinear Schrödinger equation with nonlinear dispersion GNLS(l,n,p,q). Taking advantage of the new subsidiary ODE, this F-function method is used to map the solutions of C(l,n,p) and GNLS(l,n,p,q) equations to those of that nonlinear ODE. As result, we can successfully obtain in a unified way, many exact solutions.     

Spatial averaging of oceanic rainfall variability using underwater sound: Ionian Sea rainfall experiment 2004

An experiment to evaluate the inherent spatial averaging of the underwater acoustic signal from rainfall was conducted in the winter of 2004 in the Ionian Sea southwest of Greece. A mooring with four passive aquatic listeners (PALs) at 60, 200, 1000, and 2000 m was deployed at 36.85 degrees N, 21.52 degrees E, 17 km west of a dual-polarization X-band coastal radar at Methoni, Greece. The acoustic signal is classified into wind, rain, shipping, and whale categories. It is similar at all depths and rainfall is detected at all depths. A signal that is consistent with the clicking of deep-diving beaked whales is present 2% of the time, although there was no visual confirmation of whale presence. Co-detection of rainfall with the radar verifies that the acoustic detection of rainfall is excellent. Once detection is made, the correlation between acoustic and radar rainfall rates is high. Spatial averaging of the radar rainfall rates in concentric circles over the mooring verifies the larger inherent spatial averaging of the rainfall signal with recording depth. For the PAL at 2000 m, the maximum correlation was at 3-4 km, suggesting a listening area for the acoustic rainfall measurement of roughly 30-50 km(2).     

The Radical Anions of syn-1,6:8,13-Bridged [14] Annulenes. A Compilation of Hyperfine Data

Hyperfine coupling constants and g-factors determined by ESR and ENDOR spectroscopy are given for the radical anions of 21 syn-1,6:8,13-bridged [14]annulenes. The great majority of these values is reported for the first time. The hyperfine data are consistent with the single occupancy of an orbital which resembles a π-perimeter-LUMO of the same nodal properties. The sum of the coupling constants of the protons attached to the π-perimeter can be used as a planarity criterion for this perimeter.     

Kinetics and scaling in ballistic annihilation

We study the simplest irreversible ballistically controlled reaction, whereby particles having an initial continuous velocity distribution annihilate upon colliding. In the framework of the Boltzmann equation, expressions for the exponents characterizing the density and typical velocity decay are explicitly worked out in arbitrary dimension. These predictions are in excellent agreement with the complementary results of extensive Monte Carlo and molecular dynamics simulations. We finally discuss the definition of universality classes indexed by a continuous parameter for this far from equilibrium dynamics with no conservation laws.     

Interaction of primary amphipathic cell-penetrating peptides with phospholipid-supported monolayers

The mesoscopic organization adopted by two primary amphipathic peptides, P(beta) and P(alpha), in Langmuir-Blodgett (LB) films made of either the pure peptide or peptide-phospholipid mixtures was examined by atomic force microscopy. P(beta), a potent cell-penetrating peptide (CPP), and P(alpha) mainly differ by their conformational states, predominantly a beta-sheet for P(beta) and an alpha-helix for P(alpha), as determined by Fourier transform infrared spectroscopy. LB films of pure peptide, transferred significantly below their collapse pressure, were characterized by the presence of supramolecular structures, globular aggregates for P(beta) and filaments for P(alpha), inserted into the monomolecular film. In mixed peptide-phospholipid films, similar structures could be observed, as a function of the phospholipid headgroup and acyl chain saturation. They often coexisted with a liquid-expanded phase composed of miscible peptide-lipid. These data strongly suggest that primary amphipathic CPP and antimicrobial peptides may share, to some extent, common mechanisms of interaction with membranes.