203 research outputs found
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Some Observations on the Structure of TATB
The recent discovery of second-harmonic light generation (SHG) from 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) has renewed interest in both the crystallography and the identification of defect structures in this material. The accepted crystal structure is triclinic but centrosymmetric (P-1); SHG is not expected from materials of this symmetry. A wide variety of syntheses have been shown to produce SHG-positive materials, including an emulsion technique, two different recrystallization methods, and a variety of combined reaction - precipitation processes. In addition, two standard commercial powders have shown the property after annealing in the 300 C range. We have examined the structures of several of these powders using polarized light microscopy (PLM), scanning electron microscopy (SEM), and powder X-ray diffraction (XRD). We find that SHG-positive materials typically contain crystals both more transparent and more strongly faceted (i.e. ''more perfect'') than weak-SHG ones and that the positive samples show stronger texture in their powder diffraction patterns. These results are compared with predictions from Cady's structure
Studies on Ca (II) binding to gamma-carboxyglutamic acid. Use of thermal decarboxylation to probe metal ion/gamma-carboxyglutamic acid interactions.
The thermal decarboxylation of N-benzyloxycarbonyl-L-gamma-carboxyglutamic acid alpha-methyl ester [Z)-L-Gla-OMe) has been studied. In the presence of increasing amounts of calcium or magnesium ions, lyophilized powders of (Z)-L-Gla-OMe exhibit a corresponding increase in thermal stability. Both magnesium and calcium form relatively tight, thermally stable complexes with (Z)-L-Gla-OMe at high metal ion concentrations. Differences between Ca(II) and Mg(II) binding are noted at low metal ion concentrations, where (Z)-L-Gla-OMe is in excess. Under these conditions, complex formation with Mg(II) apparently favors a 2:1 Gla-magnesium ion complex in which both Gla residues are unstable to thermal decarboxylation. Calcium ion complexes, however, are found to favor a 3:1 Gla-calcium ion complex in which 1 of the 3 Gla residues is thermally stable
Total Synthesis of Paracaseolide A
The total synthesis of paracaseolide A, a valuable cell-cycle progression inhibitor, was accomplished in 8 steps from known compounds, with 6.6% overall yield. The synthetic strategy creates strong potential for diversification
So close, yet so far away? the effects of city size, density, and growth on local civic participation
Recent studies in the U.S. context have suggested that political participation is a
function of the size and concentration of a city’s population. Most of this research focuses on the idea
that there is an optimal size and concentration of population that favors active political participation
in terms of a higher propensity to vote in local elections, contact local officials, and attend community
meetings. The conventional argument suggests a negative relationship between city size and political
participation that is mitigated to some extent by the deeper social interactions generated by increased
population density. We extend this research by also investigating the influence of population growth
on the broader concept of civic participation. Civic participation is a multidimensional concept
that requires the use of a broad set of indicators. We expand the number of measures to gauge civic
participation at the local level by including data on the formation of volunteer associations, volunteer
fire brigades and not-for-profit organizations as well as voter turnout. We test the hypotheses
derived from extant research using aggregate data collected from Portuguese cities and discuss the
implications of our findings for the literature on local civic participatio
Green primaries: Environmentally friendly energetic complexes
Primary explosives are used in small quantities to generate a detonation wave when subjected to a flame, heat, impact, electric spark, or friction. Detonation of the primary explosive initiates the secondary booster or main-charge explosive or propellant. Long-term use of lead azide and lead styphnate as primary explosives has resulted in lead contamination at artillery and firing ranges and become a major health hazard and environmental problem for both military and civilian personnel. Devices using lead primary explosives are manufactured by the tens of millions every year in the United States from primers for bullets to detonators for mining. Although substantial synthetic efforts have long been focused on the search for greener primary explosives, this unresolved problem has become a “holy grail” of energetic materials research. Existing candidates suffer from instability or excessive sensitivity, or they possess toxic metals or perchlorate. We report here four previously undescribed green primary explosives based on complex metal dianions and environmentally benign cations, (cat)(2)[M(II)(NT)(4)(H(2)O)(2)] (where cat is NH(4)(+) or Na(+), M is Fe(2+) or Cu(2+), and NT(−) is 5-nitrotetrazolato-N(2)). They are safer to prepare, handle, and transport than lead compounds, have comparable initiation efficiencies to lead azide, and offer rapid reliable detonation comparable with lead styphnate. Remarkably, they possess all current requirements for green primary explosives and are suitable to replace lead primary explosives in detonators. More importantly, they can be synthesized more safely, do not pose health risks to personnel, and cause much less pollution to the environment
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