Correlation of antioxidant depletion and mechanical performance during thermal degradation of an HTPB elastomer

Thermal degradation studies of a stabilized HTPB based elastomer were conducted at temperatures from 50 °C to 110 °C. The concentration of extractable antioxidant (AO2246) in the polymer was quantified via AO extraction and a gas chromatography-based method using internal standards. The decrease in extractable AO levels as a function of time and temperature was evaluated and correlated with mechanical property changes. Most importantly, AO depletion features were found to be temperature dependent. At elevated temperatures (>80 °C) extractable AO levels decreased rapidly and faster than the concurrent loss in mechanical properties. While extractable AO concentrations decrease quickly, the material is able to maintain some useful mechanical properties, perhaps via non-extractable or grafted AO species formed during degradation providing additional protection. At lower aging temperatures extractable or free AO levels decreased more slowly than the mechanical properties. Therefore, for condition monitoring purposes a universal correlation between AO levels and aging state or material condition could not be established. Most importantly, however, loss of mechanical properties and oxidative degradation is observed at lower temperatures despite significant levels of free antioxidant in the material. The antioxidant appears to be limited in its effectiveness to completely prevent degradation reactions, or only fractions of the total AO available are actually involved in the inhibition process.     

Stereoselective syntheses of 1,4-dideoxy-1,4-imino-octitols and novel tetrahydroxyindolizidines

A new route for the preparation of four new indolizidines, (1R,2S,6S,7S,8aS)- and (1R,2S,6R,7R,8aS)-1,2,6,7-tetrahydroxyindolizidine (30 and 32) and (1S,2R,7S,8S,8aR)- and (1S,2R,7R,8R,8aR)-1,2,7,8-tetrahydroxyindolizidine (44 and 46), is reported. The synthesis is based on Knoevenagel homologation of the readily available enantiomerically pure pyrrolidin-carbaldehydes 13 and 37followed by asymmetric dihydroxylation of the subsequent alkenyl pyrrolidines and cyclization of the corresponding imino-octitols. The new indolizidines and their precursors (imino-octitols 20, 25, 26) and indolizidinones 28a and 28b have been tested for inhibitory activities toward 26 glycosidases. The enzymatic inhibition of trans-7-hydroxy-d-(-)-swainsonine (44) toward alpha-mannosidases is similar to that described for trans-7-hydroxy-l-(+)-swainsonine (11b) toward naringinase (alpha-l-rhamnosidase from Penicillium decumbens).     

Differentiation along arbitrary orientations

A prevalent problem of mechanics is the differentiation of experimental information with respect to various directions, including the determination of cross derivatives. Simple methods for evaluating such derivatives along straight and curved directions are described. The concepts are demoinstrated at boundary and internal locations of in-plane and transversely loaded plates.     

STM-study of triangular defect structures induced on WSe2

With short voltage pulses, applied between sample and tip of a scanning tunnelling microscope, it is possible to generate a variety of defects on the surface of layered transition metal dichalcogenides. In the case of WSe₂ triangular holes can be induced with a depth of a single Se-W-Se layer that grow in lateral size during scanning. We present measurements of the time evolution of the growth and its dependence on parameters of the scanning process. Furthermore, we draw attention to the peculiar shape of the edges of such triangles where several distinct rims are found. As a possible interpretation we suggest that these are caused by an oscillating workfunction or density of states due to electron interference.     

Effect of Pr-Ca substitution on the transport and magnetic behavior of LaMnO3 perovskite

The effect of simultaneous substitution of a fluctuating cation and a divalent cation in LaMnO₃ perovskite modifies the properties of the material to exhibit large valence colossal magnetoresistance (CMR) effect. A good example of these properties is (La_1−2x Pr _x Ca _x )MnO₃ (LPCMO) type CMR material. In this communication it is reported that, with the increase in x (for x=0.1, 0.15, 0.2), the T _c varies between 100 and 120 K with improvisation in metal-insulator transition. Interestingly, resistance increases with x from few hundred ohms to few kilo ohms with corresponding decrease in the unit cell volume. The results of the studies using X-ray diffraction (XRD), electrical resistivity, magnetoresistance and ac susceptibility measurements on LPCMO samples for understanding the structural, transport and magnetic properties are discussed in detail.     

Energy transfer to a copper surface by low energy noble gas ion bombardment

The energy transferred to a copper surface by bombardment with Xe⁺, Ar⁺, and He⁺ ions with kinetic energies in the range 100–4000 eV has been studied by our group in previous experiments. There were significant experimental uncertainties for that data at energies below about 200 eV. The present investigation overlaps the previous work, extends the energy range to 10 eV, and includes data for Ne⁺. Particular emphasis is placed on the energy range below 200eV. A specially designed ion source was employed in these experiments. A polycrystalline copper film deposited onto a highly sensitive calorimeter was used as the target material. The results show that the Xe⁺ ion deposits more than 97% of its energy over the entire range investigated whereas the lighter ions deposit a decreasing fraction of their energy below about 1 keV. The decrease is largest for the lightest ion (He⁺). In all cases the deposited energy is about or more than 70% of the incident energy. It will be shown that the present results are in agreement with previous measurements for copper and are qualitatively in good agreement with computer calculations using the TRIM.SP code.On leave from: Institut für Schicht- und Ionentechnik, Forschungszentrum Jülich GmbH, W-5170 Jülich, Fed. Rep. Germany     

A Chemiluminescent Probe for HNO Quantification and Real‐Time Monitoring in Living Cells

Azanone (HNO) is a reactive nitrogen species with pronounced biological activity and high therapeutic potential for cardiovascular dysfunction. A critical barrier to understanding the biology of HNO and furthering clinical development is the quantification and real‐time monitoring of its delivery in living systems. Herein, we describe the design and synthesis of the first chemiluminescent probe for HNO, HNOCL‐1 , which can detect HNO generated from concentrations of Angeli's salt as low as 138 nm with high selectivity based on the reaction with a phosphine group to form a self‐cleavable azaylide intermediate. We have capitalized on this high sensitivity to develop a generalizable kinetics‐based approach, which provides real‐time quantitative measurements of HNO concentration at the picomolar level. HNOCL‐1 can monitor dynamics of HNO delivery in living cells and tissues, demonstrating the versatility of this method for tracking HNO in living systems.