Characterization of cyclotetramethylenetetranitramine (HMX) thermal degradation by isotope analyses with analytical pyrolysis-atmospheric pressure ionization tandem mass spectrometry

Analytical pyrolysis-atmospberic pressure ionization (Py-API) tandem mass Spectrometry was used in the structure elucidation of the oxidalive and non-oxidative thermal decomposition products of cyclotetramethylenetetranitramine (HMX). The [¹⁵NO₂]-, [¹⁵N₈]- and [²H₈]-HMX isotope preparations provided fundamental information in the determination of the identities of the various pyrolyzate species. All RDX pyrolysis product ions that were identified by Py-API tandem mass Spectrometry, i.e. m/z 44, 60, 74, 75, 85 and 98, were present in the pyrolyzate of HMX. In both RDX and HMX investigations, these ions provided identical mass spectral daughter ion analyses. HMX, however, provided additional ions at m/z 30, 58, 69, 71, 83 and 141. Of all thirteen ions identified in the Py-APJ mass spectrum of HMX, only that at m/z 75 contained a nitrogen atom that originated from the NO₂ group. Standards analysis confirmed the identities of the ions at m/z 69, 71 and 141 as methyleneaminoacetonitrile, methylaminoacetonitrile and the caged compound hoxamethylenetetraamine, respectively. Isotopic analyses provided a high degree of confidence on the structural assignments of the ions at m/z 30 and 58 as methyleneimine and methyleneformamide; the ion at m/z 83, however, appeared to be a heterocyclic compound with daughter ion mass spectral elements similar to but not identical with that of 1-methylimidazole and 3-methylpyrazole.     

Carrier-free estimation of106Ru in urine

A simple carrier-free method has been developed for estimating 0.1 to 1.1 Bq of¹⁰⁶Ru in urine. The organic matter present in urine samples was completely destroyed by wet ashing using nitric acid-peroxide mixture in presence of sulfuric acid. Ruthenium was oxidized to tetroxide using potassium periodate and allowed to react in-situ with polyethylene powder. The powder was separated, washed, pelletized and its -activity was counted. Recovery of¹⁰⁶Ru is found to be better than 80% with a minimum detection limit of 0.2 Bq/dm³ which is less than the DRL value specified by International Commission on Radiological Protection (ICRP).     

Two new macrocyclic diaryl ether heptanoids from Boswellia ovalifoliolata

The stems of Boswellia ovalifoliolata BAL. & HENRY (Burseraceae) afforded two new macrocyclic diaryl ether heptanoids, ovalifoliolatin A (1) and B (2) together with three known compounds; acerogenin C (3), 3 alpha-hydroxyurs-12-ene (4), and sitost-4-en-3-one (5). The structures were established by means of spectroscopic analysis and compounds 1, 3-5 were evaluated for their antibacterial activity.     

Studies on the interference of EDTA in the titrimetric determination of iron(II)

Summary Suitability of vanadium(V), manganese(VII), cerium(IV) and chromium(VI), as oxidants in the titration of iron(II) in the presence of EDTA has been investigated and vanadium(V) has been found to be the best one for that purpose, as titration with this reagent is not influenced by any interference. Cerium(IV) can be used provided phosphoric acid or bismuth nitrate is added to eliminate the interference by EDTA. Chromium(VI) is useful only in the presence of bismuth salt. This effect of bismuth nitrate is not observed in hydrochloric acid medium. Manganese(VII) cannot be used even in the presence of bismuth nitrate, since manganese(II) catalyses the reaction between manganese(VII) and even the metal bound EDTA. Optimum conditions for the quantitative photochemical reduction of iron(III) by EDTA are established.

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Zusammenfassung Die Eignung von V^V,Mn^VII,Ce^IV und Cr^VI zur Titration von Eisen(II) in Gegenwart von ÄDTA ist untersucht worden. V^V hat sich am besten bewährt und ist keinen Störungen ausgesetzt. Ce^IV kann bei Zusatz von Phosphorsäure oder Wismutnitrat benutzt werden. Cr^VI nur bei Gegenwart von Wismutsalz. Die Wirkung von Wismutnitrat konnte in salzsaurem Medium nicht beobachtet werden. Mn^VII kann auch bei Gegenwart von Wismutsalz nicht verwendet werden, da Mn^II sogar die Reaktion zwischen Mn^VII und dem metallgebundenen ÄDTA katalysiert. Die optimalen Bedingungen für die quantitative photochemische Reduktion von Eisen(III) mit ÄDTA wurden ausgearbeitet.

     

Effect of ventilation on the flowfield around a sphere

The flowfield around a sphere with and without ventilation was investigated in a wind tunnel over a range of Reynolds numbers in an incompressible flow. At supercritical Re, the pressure drag of a sphere can be nearly nullified by venting only 2% of the frontal area of the sphere to the base through a smooth internal duct. The drag reduction is achieved by increased pressures in the separated flow region close to the base. At high Re, the vent flow breaks through the near wake and brings about symmetry in the global flowfield. When the internal shear is increased by using a rough internal duct, the base pressure is unchanged, but the external flow is accelerated to velocities beyond that achieved by the potential flow around the basic sphere. The findings can be explained by a flow model in which the near wake is aerodynamically streamlined by a pair of counterrotating vortex rings at the base. A roughness element can be made to partially destroy the vortex system at the base and result in a steady asymmetric wake. A 1.2 mm diameter wire placed at 70° was found to overtrip the boundary layer and completely destroy the vortex system. Simultaneously, the turbulent separation is advanced and the drag increased.At subcritical Re, ventilation marginally increases static pressures all over the surface. Since the large pressure differential between the windward and leeward sides is not reduced, the internal flow has a rapid acceleration to a velocity close to that of the free stream. The reverse flow associated with the near wake forces the vent flow to rest within itself and the wake profile is unchanged. The main features of subcritical flow around the basic sphere are retained in spite of ventilation. The upstream effects of ventilation are greater for subcritical flow than for supercritical flow.The work reported was carried out under a study grant from the German Academic Exchange Service (DAAD) in Bonn. The authors wish to thank the Director of DAAD in Bonn for the same. Thanks are due to Dr. F. R. Grosche and colleagues at DLR in Göttingen who assisted in the design, fabrication and wind tunnel testing of the sphere model. Thanks are also due to Prof. D. G. Mabey, visiting Professor, Imperial College, London for useful discussions. The many useful discussions with the research advisors of the first author viz., Dr. P. R. Viswanath of National Aerospace Laboratories and Prof. A. Prabhu of Indian Institute of Science, Bangalore are acknowledged with thanks. The support given by the Head, Experimental Aerodynamics Division, National Aerospace Laboratories is thankfully acknowledged.     

Upper semicontinuity of set-valued functions

Various types of upper semcontinuity properties for set-valued functions have been used in the past to obtain closure and lower closure theorems in optimal control theory as well as selection theorems and fixed-point theorems in topology. This paper unifies these various concepts by using semiclosure operators, extended topologies, and lattice theoretic operations and obtains general closure theorems. In addition, analytic criteria are given for this generalized upper semicontinuity. In particular, set-valued functions which are maximal in terms of certain properties (e.g., maximal monotone multifunctions) are shown to be necessarily upper semicontinuous.     

Closure theorems without seminormality conditions

The authors give a variety of conditions under which there is no need to explicity require seminormality conditions in closure and lower closure theorems, and corresponding lower semicontinuity theorems. Both Lipschitz-type conditions and growth-type conditions are taken into consideration in classesL _p andL _∞ .     

Strength and stiffness of sandwich beams in bending

This investigation is concerned with the experimental versus analytical correlation of the mechanical properties of sandwich-beam specimens. Such sandwich structures are commonly employed in the aircraft industry. Four-point and three-point load tests were conducted on a large number of sandwich-beam specimens, fabricated by using fiber-glass reinforced plastics (both unidirectional and woven-glass cloth) and DTD 685 aluminum alloy for the facings with aluminum honeycomb core and polyurethane foam cores and the indigenously available Araldite as the bonding medium between the core and the facings.The flexural stiffness of the composite sandwich specimens used in this investigation compared favorably with theoretical predictions. The shear stiffness was found to be about 55 percent and 45 percent of the theoretically predicted values for FRP (fiberglass-reinforced-plastic) cloth and FRP unidirectional laminates with aluminum honeycomb core sandwich, respectively. The failure load as determined by experiments was less than the theoretically predicted safe load. There was a loss of strength as well as a steep decrease in the failure load in the case of low density foam core.It was concluded that FRP facing plates with aluminum honeycomb core sandwich structure may be preferred to similar aluminum-alloy facing sandwich construction if high flexural stiffness and shear stiffness properties are required at less cost and weight. Indigenously available Araldite was quite satisfactory for bonding the core to the facings.This investigation has confirmed the importance of experiments in the field of sandwich structures which can effectively replace other conventional uneconomical structural or machine members which are currently in use.     

Multilevel Monte Carlo simulation for Lévy processes based on the Wiener–Hopf factorisation

In Kuznetsov et al. (2011) a new Monte Carlo simulation technique was introduced for a large family of Lévy processes that is based on the Wiener–Hopf decomposition. We pursue this idea further by combining their technique with the recently introduced multilevel Monte Carlo methodology. Moreover, we provide here for the first time a theoretical analysis of the new Monte Carlo simulation technique in Kuznetsov et al. (2011) and of its multilevel variant for computing expectations of functions depending on the historical trajectory of a Lévy process. We derive rates of convergence for both methods and show that they are uniform with respect to the “jump activity” (e.g. characterised by the Blumenthal–Getoor index). We also present a modified version of the algorithm in Kuznetsov et al. (2011) which combined with the multilevel methodology obtains the optimal rate of convergence for general Lévy processes and Lipschitz functionals. This final result is only a theoretical one at present, since it requires independent sampling from a triple of distributions which is currently only possible for a limited number of processes.