Oxygen evolution on La0.5Ba0.5CoO3: Transient measurements

The recovery behavior of an aged La_0.5Ba_0.5CoO₃ electrode after interrupting a cathodic discharge current (forced decay, all starting from a high prepolarized state) at a still positive overpotential of 150 mV is discussed. It was found that the potential rises again after interrupting the cathodic current. This rise in potential decreases with decreasing cathodic currents when the electrodes are stabilized at the same starting overpotential before applying the cathodic current. The rise in potential also decreases with decreasing starting overpotential for the same cathodic discharge current. From these measurements it was concluded that higher oxides are present to a certain depth in the oxide layer at high positive overpotentials.Open-circuit decay measurements with different starting overpotentials were performed, all showing logarithmic slopes of ～ 50 mV/dec. The decay rates increased for lower starying overpotentials. Impedances were measured during a decay, from which effective capacitances were calculated. For a given overpotential, the capacitances during a decay were practically constant in the overpotential range from 220 to 150 mV for a given staring overpontential. But for higher starting overpotentials the capacitances were found to be higher. These effects are explained by a change in effective surface area for different starting overpotentials caused by the above-mentioned higher oxides blocking the surface.     

Topological classification and structural stability of linear systems

In this paper it is shown that the linear systems Σ_i defined by $\text{Σ}{}_{\mathrm{i}}\text{:}\text{x}\text{?}{}_{\mathrm{i}}\text{= A}{}_{\mathrm{i}}\text{x}{}_{\mathrm{i}}\text{+ B}{}_{\mathrm{i}}\text{u}{}_{\mathrm{i}}\text{, i = 1, 2}$, are topologically equivalent if and only if they have the same Kronecker indices and the flows defined by considering trajectories modulo their controllable subspace are topologically equivalent. From some recent work of N. H. Kuiper (in “Manifolds—Tokyo 1973,” Univ. of Tokyo Press, Tokyo 1975) it is known exactly what this last condition amounts to. With these results at hand it is then not difficult to investigate the structural stability of $\text{∑:}\text{x}\text{?}\text{= Ax + Bu}$ and, in fact, structural stability turns out to be generic.     

Analysis of a series of chlorogenic acid isomers using differential ion mobility and tandem mass spectrometry

Chlorogenic acids are among the most abundant phenolics found in the human diet. Of these, the mono-caffeoylquinic acids are the predominant phenolics found in fruits, such as apples and pears, and products derived from them. In this research, a comprehensive study of the electrospray ionization (ESI) tandem mass spectrometric (MS/MS) dissociation behavior of the three most common mono-caffeoylquinic acids, namely 5-O-caffeoylquinic acid (5-CQA), 3-O-caffeoylquinic acid (3-CQA) and 4-O-caffeoylquinic acid (4-CQA), were determined using both positive and negative ionization. All proposed structures of the observed product ions were confirmed with second-generation MS³ experiments. Similarities and differences between the dissociation pathways in the positive and negative ion modes are discussed, confirming the proposed structures and the established MS/MS fingerprints. MS/MS dissociation was primarily driven via the cleavage of the ester bond linking the quinic acid moiety to the caffeic acid moiety within tested molecules. Despite being structural isomers with the same m/z values and dissociation behaviors, the MS/MS data in the negative ion mode was able to differentiate the three isomers based on ion intensity for the major product ions, observed at m/z 191, 179 and 173. This differentiation was consistent among various MS instruments. In addition, ESI coupled with high-field asymmetric waveform ion mobility spectrometry-mass spectrometry (ESI-FAIMS-MS) was employed for the separation of these compounds for the first time. By combining MS/MS data and differential ion mobility, a method for the separation and identification of mono-caffeoylquinic in apple/pear juice samples was developed with a run time of less than 1 min. It is envisaged that this methodology could be used to identify pure juices based on their chlorogenic acid profile (i.e., metabolomics), and could also be used to detect juice-to-juice adulteration (e.g., apple juice addition to pear juice).     

Discovery of a potent and highly β1 specific proteasome inhibitor from a focused library of urea-containing peptide vinyl sulfones and peptide epoxyketones

Syringolins, a class of natural products, potently and selectively inhibit the proteasome and show promising antitumour activity. To gain insight in the mode of action of syringolins, the ureido structural element present in syringolins is incorporated in oligopeptide vinyl sulfones and peptide epoxyketones yielding a focused library of potent new proteasome inhibitors. The distance of the ureido linkage with respect to the electrophilic trap strongly influences subunit selectivity within the proteasome. Compounds 13 and 15 are β5 selective and their potency exceeds that of syringolin A. In contrast, 5 may well be the most potent β1 selective compound active in living cells reported to date.     

The trivial intersection problem for characters of principal indecomposable modules

For a prime p and a finite group G let Φ_p(G) denote the complex character associated to the projective indecomposable module in characteristic p with trivial head. Let Irr(Φ_p(G)) denote the set of irreducible characters occurring as constituents in Φ_p(G). We characterize all finite simple groups which satisfy Irr(Φ_p(G))∩Irr(Φ_q(G))={1_G} for all primes p≠q.     

Whistling of a pipe system with multiple side branches: Comparison with corrugated pipes

Corrugated pipes are widely used because they combine local rigidity with global flexibility. Whistling induced by flow through such pipes can lead to serious environmental and structural problems. The whistling of a multiple side branch system is compared to the whistling behavior of corrugated pipes. The study has been restricted to cavities with sharp edges which are convenient for theoretical modeling. The side branch depth is chosen to be equal to the side branch diameter, which corresponds to cavity geometries in typical corrugated pipes. The low frequency resonance modes of the multiple side branch system have been predicted by means of acoustic models, of which the validity has been tested experimentally. Several experiments have been carried out for characterizing the whistling behavior of the system. While the behavior of a multiple side branch system is interesting on its own it can be compared to that of corrugated pipes. These experiments show that the multiple side branch system is in many aspects a reasonable model for corrugated pipes. Advantage of the multiple side branch system is that it is an experimental setup allowing easy modification of cavity depth. We used this feature to identify the pressure nodes of the acoustic standing wave along the main pipe as the regions where sound is produced. This contradicts recent publications on corrugated pipes. Another interesting aspects is that the system appears to whistle at the second hydrodynamic mode of the cavities rather than at the first hydrodynamic mode. A prediction model for the whistling behavior is proposed, consisting of an energy balance, based on the vortex sound theory. The model predicts the observed Strouhal number but overestimates the acoustic fluctuation amplitude by a factor four.