Quinol-containing ligands enable high superoxide dismutase activity by modulating coordination number,charge, oxidation states and stability of manganese complexes throughout redox cycling

Reactivity assays previously suggested that two quinol-containing MRI contrast agent sensors for H₂O₂, [Mn(H2qp1)(MeCN)]²⁺ and [Mn(H4qp2)Br₂], could also catalytically degrade superoxide. Subsequently, [Zn(H2qp1)(OTf)]⁺ was found to use the redox activity of the H2qp1 ligand to catalyze the conversion of O₂˙⁻ to O₂ and H₂O₂, raising the possibility that the organic ligand, rather than the metal, could serve as the redox partner for O₂˙⁻ in the manganese chemistry. Here, we use stopped-flow kinetics and cryospray-ionization mass spectrometry (CSI-MS) analysis of the direct reactions between the manganese-containing contrast agents and O₂˙⁻ to confirm the activity and elucidate the catalytic mechanism. The obtained data are consistent with the operation of multiple parallel catalytic cycles, with both the quinol groups and manganese cycling through different oxidation states during the reactions with superoxide. The choice of ligand impacts the overall charges of the intermediates and allows us to visualize complementary sets of intermediates within the catalytic cycles using CSI-MS. With the diquinolic H4qp2, we detect Mn(iii)-superoxo intermediates with both reduced and oxidized forms of the ligand, a Mn(iii)-hydroperoxo compound, and what is formally a Mn(iv)-oxo species with the monoquinolate/mono-para-quinone form of H4qp2. With the monoquinolic H2qp1, we observe a Mn(ii)-superoxo ↔ Mn(iii)-peroxo intermediate with the oxidized para-quinone form of the ligand. The observation of these species suggests inner-sphere mechanisms for O₂˙⁻ oxidation and reduction that include both the ligand and manganese as redox partners. The higher positive charges of the complexes with the reduced and oxidized forms of H2qp1 compared to those with related forms of H4qp2 result in higher catalytic activity (k_cat ∼ 10⁸ M⁻¹ s⁻¹ at pH 7.4) that rivals those of the most active superoxide dismutase (SOD) mimics. The manganese complex with H2qp1 is markedly more stable in water than other highly active non-porphyrin-based and even some Mn(ii) porphyrin-based SOD mimics.

Manganese complexes with polydentate quinol-containing ligands are found to catalyze the degradation of superoxide through inner-sphere mechanisms. The redox activity of the ligand stabilizes higher-valent manganese species.     

Application of displacement chromatography for the proteome analysis of a human plasma protein fraction

It was the aim of this study to compare the performance of displacement chromatography with gradient elution chromatography both applied as the cation-exchange separation step for a proteome analysis in a bottom-up approach using multidimensional chromatography for the separation of tryptic peptides prior to their mass spectrometric analysis. The tryptic digest of the human Cohn fraction IV-4 served as a sample. For both chromatography modes commonly used operating parameters were chosen thus ensuring optimal separation results of equal sample amounts for each mode. All resulting fractions were analyzed with an HPLC-chip–LC–MS system. The eluate of the HPLC-chip column was ionized by electrospray ionization (ESI) and analyzed with an ion-trap mass spectrometer. For guaranteeing high confidence concerning the identity of the peptides, the mass spectrometric data were processed by different bioinformatic tools applying stringent criteria. By the displacement approach the total amount of identified proteins (78) was significantly higher than in the gradient mode (58). The results showed that displacement chromatography is a well suited alternative in comparison to gradient elution separation for analysis of proteomes via the bottom-up approach applying multidimensional chromatography, especially in those cases when larger quantities of proteins are available.     

Shift operators contained in contractions, pseudocontinuable Schur functions and orthogonal systems on the unit circle

The main aim of this paper is to establish the connection between well-known criteria for the pseudocontinuability of a non-inner Schur function ?? in the unit disk (see Theorems 3.9, 4.2). In a canonical way we associate a probability measure ?? on the unit circle with ??. One of the two criteria will be reformulated in the face of ??, whereas the other one is drafted in view of a completely nonunitary contraction T having ?? as corresponding characteristic function. Our main result clarifies an immediate connection between the above-mentioned two criteria. In this way, we rewrite these criteria in terms of orthogonal systems with respect to the measure ?? (see Theorem 7.2).     

Time-reversal multiple signal classification in case of noise: a phase-coherent approach

The problem of locating point-like targets beyond the classical resolution limit is revisited. Although time-reversal MUltiple SIgnal Classification (MUSIC) is known for its super-resolution ability in localization of point scatterers, in the presence of noise this super-resolution property will easily break down. In this paper a phase-coherent version of time-reversal MUSIC is proposed, which can overcome this fundamental limit. The algorithm has been tested employing synthetic multiple scattering data based on the Foldy-Lax model, as well as experimental ultrasound data acquired in a water tank. Using a limited frequency band, it was demonstrated that the phase-coherent MUSIC algorithm has the potential of giving significantly better resolved scatterer locations than standard time-reversal MUSIC.     

Relativity and the lead-acid battery

The energies of the solid reactants in the lead-acid battery are calculated ab?initio using two different basis sets at nonrelativistic, scalar-relativistic, and fully relativistic levels, and using several exchange-correlation potentials. The average calculated standard voltage is 2.13?V, compared with the experimental value of 2.11?V. All calculations agree in that 1.7-1.8?V of this standard voltage arise from relativistic effects, mainly from PbO2 but also from PbSO4.     

Simultaneous measurements of multiple flow velocity components using frequency modulated lasers and a single molecular absorption cell

Since unsteady, complex flow phenomena play an important role, optical measurements techniques are required for flow investigations, which provide simultaneous measurements of multiple velocity components. Doppler global velocimetry has this potential. It is a flow measurement technique, where the Doppler shift of scattered light is measured by a molecular absorption cell for frequency-to-intensity conversion. However, novel Doppler global velocimeters with laser frequency modulation were only used for single component measurements yet. In order to enhance such a system for the simultaneous measurement of multiple components, a concept based on frequency division multiplexing is introduced for the first time. Besides multiple lasers, only a single molecular absorption cell and a single detector unit is required. Two-component measurements of velocity profiles from nozzle flows are presented as a proof of principle. The designed measurement system provides high measurement rates of up to 20 kHz, which is three orders of magnitude higher than for typical Doppler global velocimetry setups.     

Highly efficient single-pass source of pulsed single-mode twin beams of light

We report the realization of a bright ultrafast type II parametric down-conversion source of twin beams free of any spatiotemporal correlations in a periodically poled KTiOPO4 (PP-KTP) waveguide. From a robust, single-pass setup it emits pulsed two-mode squeezed vacuum states: photon-number entangled pairs of single-mode pulses or, in terms of continuous variables quantum optics, pulsed Einstein-Podolsky-Rosen states in the telecom wavelength regime. We verify the single-mode character of our source by measuring Glauber correlation functions g(2) and demonstrate with a pump energy as low as 75 pJ per pump pulse a mean photon number of 2.5.     

Unveiling the nature of three-dimensional orbital ordering transitions: the case of e(g) and t(2g) models on the cubic lattice

We perform large scale finite-temperature Monte Carlo simulations of the classical e(g) and t(2g) orbital models on the simple cubic lattice in three dimensions. The e(g) model displays a continuous phase transition to an orbitally ordered phase. While the correlation length exponent ν ≈ 0.66(1) is close to the 3D XY value, the exponent η ≈ 0.15(1) differs substantially from O(N) values. At T(c) a U(1) symmetry emerges, which persists for T < T(c) below a crossover length scaling as Λ ～ ξ(a), with an unusually small a ≈ 1.3. Finally, for the t(2g) model we find a first order transition into a low-temperature lattice-nematic phase without orbital order.     

All nonclassical correlations can be activated into distillable entanglement

We devise a protocol in which general nonclassical multipartite correlations produce a physically relevant effect, leading to the creation of bipartite entanglement. In particular, we show that the relative entropy of quantumness, which measures all nonclassical correlations among subsystems of a quantum system, is equivalent to and can be operationally interpreted as the minimum distillable entanglement generated between the system and local ancillae in our protocol. We emphasize the key role of state mixedness in maximizing nonclassicality: Mixed entangled states can be arbitrarily more nonclassical than separable and pure entangled states.