A new model for magnesium chemistry in the upper atmosphere

This paper describes the kinetic study of a number of gas-phase reactions involving neutral Mg-containing species, which are important for the chemistry of meteor-ablated magnesium in the upper mesosphere/lower thermosphere region. The study is motivated by the very recent observation of the global atomic Mg layer around 90 km, using satellite-born UV-visible spectroscopy. In the laboratory, Mg atoms were produced thermally in the upstream section of a fast flow tube and then converted to the molecular species MgO, MgO(2), OMgO(2), and MgCO(3) by the addition of appropriate reagents. Atomic O was added further downstream, and Mg was detected at the downstream end of the flow tube by laser-induced fluorescence. The following rate coefficients were determined at 300 K: k(MgO + O → Mg + O(2)) = (6.2 ± 1.1) × 10(-10); k(MgO(2) + O → MgO + O(2)) = (8.4 ± 2.8) × 10(-11); k(MgCO(3) + O → MgO(2) + CO(2)) ≥ 4.9 × 10(-12); and k(MgO + CO → Mg + CO(2)) = (1.1 ± 0.3) × 10(-11) cm(3) molecule(-1) s(-1). Electronic structure calculations of the relevant potential energy surfaces combined with RRKM theory were performed to interpret the experimental results and also to explore the likely reaction pathways that convert MgCO(3) and OMgO(2) into long-lived reservoir species such as Mg(OH)(2). Although no reaction was observed in the laboratory between OMgO(2) and O, this is most likely due to the rapid recombination of O(2) with the product MgO(2) to form the relatively stable O(2)MgO(2). Indeed, one significant finding is the role of O(2) in the mesosphere, where it initiates holding cycles by recombining with radical species such as MgO(2) and MgOH. A new atmospheric model was then constructed which combines these results together with recent work on magnesium ion-molecule chemistry. The model is able to reproduce satisfactorily some of the key features of the Mg and Mg(+) layers, including the heights of the layers, the seasonal variations of their column abundances, and the unusually large Mg(+)/Mg ratio.     

Interpretation of parameters in phase field models for fracture

Phase field fracture models typically feature a length parameter, which controls the width of the diffuse transition zone between broken and undamaged material. In the limit case of a vanishing length parameter, these models converge to a sharp crack formulation. From this point of view, the length scale parameter is a purely auxiliary numerical quantity. However, the study of the stability of homogeneous solutions in a one dimensional setting permits a different interpretation. Since the length parameter is directly related to the critical stress at which the homogeneous solution becomes unstable and crack nucleation occurs, it can be related to the strength of the material. In this regard, the length parameter itself may be seen as a material parameter. These analytical findings are approved by finite element simulations. (© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Enhancing the emergence rate of coherent wavefronts from ocean ambient noise correlations using spatio-temporal filters

Extracting coherent wavefronts between passive receivers using cross-correlations of ambient noise (CAN) provides a means for monitoring the seismoacoustic environment without using active sources. However, using cross-correlations between single receivers can require a long recording time in order to extract stable coherent arrivals from CAN. This becomes an issue if the propagation medium fluctuates significantly during the recording period. To address this issue, this article presents a general spatio-temporal filtering procedure to enhance the emergence rate for coherent wavefronts extracted from time-averaged ambient noise correlations between two spatially separated arrays. The robustness of this array-based CAN technique is investigated using ambient shipping noise recorded over 24?h in the frequency band [250-850 Hz] on two vertical line arrays deployed 143?m apart in shallow water (depth 20?m). Experimental results confirm that the array-based CAN technique can significantly reduce the recording duration (e.g., from 22?h to 30?min) required for extracting coherent wavefronts of sufficient amplitude (e.g., 20?dB over residual temporal fluctations) when compared to conventional CAN implementations between single pairs of hydrophones. These improvements of the CAN technique could benefit the development of noise-based ocean monitoring applications such as passive acoustic tomography.     

Dual Electroactivity in a Covalent Organic Network with Mechanically Interlocked Pillar[5]arenes

The synthesis and characterization of a polyrotaxanated covalent organic network (CON) based on the association between the viologen and pillar[5]arene (P[5]OH) units are reported. The mechanical bond allows for the irreversible insertion of n-type redox centers (P[5]OH macrocycles) within a pristine structure based on p-type viologen redox centers. Both redox units are active on a narrow potential range and, in water, the presence of P[5]OH greatly increases the electroactivity of the material.     

An Aldehyde Responsive,Cleavable Linker for Glucose Responsive Insulins

A glucose responsive insulin (GRI) that responds to changes in blood glucose concentrations has remained an elusive goal. Here we describe the development of glucose cleavable linkers based on hydrazone and thiazolidine structures. We developed linkers with low levels of spontaneous hydrolysis but increased level of hydrolysis with rising concentrations of glucose, which demonstrated their glucose responsiveness in vitro. Lipidated hydrazones and thiazolidines were conjugated to the LysB29 side-chain of HI by pH-controlled acylations providing GRIs with glucose responsiveness confirmed in vitro for thiazolidines. Clamp studies showed increased glucose infusion at hyperglycemic conditions for one GRI indicative of a true glucose response. The glucose responsive cleavable linker in these GRIs allow changes in glucose levels to drive the release of active insulin from a circulating depot. We have demonstrated an unprecedented, chemically responsive linker concept for biopharmaceuticals.     

Untersuchung der Königskerzenblüten (Flores verbasci)

Ohne Zusammenfassung