2-Hydrazonyl-Propandihydrazide - A Versatile Precursor for High-Energy Materials

In this work, 2-hydrazonyl-propandihydrazide (2), a new precursor for energetic materials based on diethyl 2,2-diazidomalonate (1) was investigated. Therefore, its versatility was shown by various secondary reactions, including formation of energetic salts (3-5), the synthesis of a nitrogen-rich bistriazole (10) and a highly instable diazido derivative (6). In addition, a Curtius degradation could be observed in detail. When possible, the compounds were analyzed by low temperature X-ray diffraction. All measurable compounds were analyzed by H-1 and C-13 NMR spectroscopy, elemental analysis, differential thermal analysis (DTA) and regarding their sensitivity towards impact and friction according to BAM standard techniques. All promising compounds were evaluated regarding their energetic behavior using the EXPLO5 code (V6.05) and compared to RDX and CL-20. In addition, compound 2 was investigated towards its aquatic toxicity, using the bioluminescent bacteria vibrio fischeri

Ten-Micron Observations of Nearby Young Stars

(abridged) We present new 10-micron photometry of 21 nearby young stars obtained at the Palomar 5-meter and at the Keck I 10-meter telescopes as part of a program to search for dust in the habitable zone of young stars. Thirteen of the stars are in the F-K spectral type range ("solar analogs"), 4 have B or A spectral types, and 4 have spectral type M. We confirm existing IRAS 12-micron and ground-based 10-micron photometry for 10 of the stars, and present new insight into this spectral regime for the rest. Excess emission at 10 micron is not found in any of the young solar analogs, except for a possible 2.4-sigma detection in the G5V star HD 88638. The G2V star HD 107146, which does not display a 10-micron excess, is identified as a new Vega-like candidate, based on our 10-micron photospheric detection, combined with previously unidentified 60-micron and 100-micron IRAS excesses. Among the early-type stars, a 10-micron excess is detected only in HD 109573A (HR 4796A), confirming prior observations; among the M dwarfs, excesses are confirmed in AA Tau, CD -40 8434, and Hen 3-600A. A previously suggested N band excess in the M3 dwarf CD -33 7795 is shown to be consistent with photospheric emission.Comment: 40 pages, 4 figures, 5 tables. To appear in the January 1, 2004 issue of Ap

Bioactive Endophytes Warrant Intensified Exploration and Conservation

A key argument in favor of conserving biodiversity is that as yet undiscovered biodiversity will yield products of great use to humans. However, the link between undiscovered biodiversity and useful products is largely conjectural. Here we provide direct evidence from bioassays of endophytes isolated from tropical plants and bioinformatic analyses that novel biology will indeed yield novel chemistry of potential value.We isolated and cultured 135 endophytic fungi and bacteria from plants collected in Peru. nrDNAs were compared to samples deposited in GenBank to ascertain the genetic novelty of cultured specimens. Ten endophytes were found to be as much as 15–30% different than any sequence in GenBank. Phylogenetic trees, using the most similar sequences in GenBank, were constructed for each endophyte to measure phylogenetic distance. Assays were also conducted on each cultured endophyte to record bioactivity, of which 65 were found to be bioactive.The novelty of our contribution is that we have combined bioinformatic analyses that document the diversity found in environmental samples with culturing and bioassays. These results highlight the hidden hyperdiversity of endophytic fungi and the urgent need to explore and conserve hidden microbial diversity. This study also showcases how undergraduate students can obtain data of great scientific significance

Prognostic Value of [18F]-Fluoro-Deoxy-Glucose PET/CT, S100 or MIA for Assessment of Cancer-Associated Mortality in Patients with High Risk Melanoma

PURPOSE: To assess the prognostic value of FDG PET/CT compared to the tumor markers S100B and melanoma inhibitory activity (MIA) in patients with high risk melanoma. METHODS: Retrospective study in 125 consecutive patients with high risk melanoma that underwent FDG PET/CT for re-staging. Diagnostic accuracy and prognostic value was determined for FDG PET/CT as well as for S100B and MIA. As standard of reference, cytological, histological, PET/CT or MRI follow-up findings as well as clinical follow-up were used. RESULTS: Of 125 patients, FDG PET/CT was positive in 62 patients. 37 (29.6%) patients had elevated S100B (>100 pg/ml) and 24 (20.2%) had elevated MIA (>10 pg/ml) values. Overall specificities for FDG PET/CT, S100B and MIA were 96.8% (95% CI, 89.1% to 99.1%), 85.7% (75.0% to 92.3%), and 95.2% (86.9% to 98.4%), corresponding sensitivities were 96.8% (89.0% to 99.1%), 45.2% (33.4% to 55.5%), and 36.1% (25.2% to 48.6%), respectively. The negative predictive values (NPV) for PET/CT, S100B, and MIA were 96.8% (89.1% to 99.1%), 61.4% (50.9% to 70.9%), and 60.6% (50.8% to 69.7%). The positive predictive values (PPV) were 96.7% (89.0% to 99.1%), 75.7% (59.9% to 86.6%), and 88.0% (70.0% to 95.8%). Patients with elevated S100B- or MIA values or PET/CT positive findings showed a significantly (p<0.001 each, univariate Cox regression models) higher risk of melanoma associated death which was increased 4.2-, 6.5- or 17.2-fold, respectively. CONCLUSION: PET/CT has a higher prognostic power in the assessment of cancer-associated mortality in melanoma patients compared with S100 and MIA

Numerical Simulations of Gravity Waves Imaged Over Arecibo During the 10-Day January 1993 Campaign

Recently, measurements were made of mesospheric gravity waves in the OI (5577 Å) nightglow observed from Arecibo, Puerto Rico, during January 1993 as part of a special 10-day campaign. Clear, monochromatic gravity waves were observed on several nights. By using a full-wave model that realistically includes the major physical processes in this region, we have simulated the propagation of two waves through the mesopause region and calculated the O(1 S) nightglow response to the waves. Mean winds derived from both UARS wind imaging interferometer (WINDII) and Arecibo incoherent scatter radar observations were employed in the computations as were the climatological zonal winds defined by COSPAR International Reference Atmosphere 1990 (CIRA). For both sets of measured winds the observed waves encounter critical levels within the O(1 S) emission layer, and wave amplitudes, derived from the requirement that the simulated and observed amplitudes of the O(1 S) fluctuations be equal, are too large for the waves to be gravitationally stable below the emission layer. Some of the model coefficients were adjusted in order to improve the agreement with the measurements, including the eddy diffusion coefficients and the height of the atomic oxygen layer. The effect of changing the chemical kinetic parameters was investigated but was found to be unimportant. Eddy diffusion coefficients that are 10 to 100 times larger than presently accepted values are required to explain most of the observations in the cases that include the measured background winds, whereas the observations can be modeled using the nominal eddy diffusion coefficients and the CIRA climatological winds. Lowering the height of the atomic oxygen layer improved the simulations slightly for one of the simulated waves but caused a less favorable simulation for the other wave. For one of the waves propagating through the WINDII winds the simulated amplitude was too large below 82 km for the wave to be gravitationally stable, in spite of the adjustments made to the model parameters. This study demonstrates that an accurate description of the mean winds is an essential requirement for a complete interpretation of observed wave-driven airglow fluctuations

Genomic Analysis of the Hydrocarbon-Producing, Cellulolytic, Endophytic Fungus Ascocoryne sarcoides

The microbial conversion of solid cellulosic biomass to liquid biofuels may provide a renewable energy source for transportation fuels. Endophytes represent a promising group of organisms, as they are a mostly untapped reservoir of metabolic diversity. They are often able to degrade cellulose, and they can produce an extraordinary diversity of metabolites. The filamentous fungal endophyte Ascocoryne sarcoides was shown to produce potential-biofuel metabolites when grown on a cellulose-based medium; however, the genetic pathways needed for this production are unknown and the lack of genetic tools makes traditional reverse genetics difficult. We present the genomic characterization of A. sarcoides and use transcriptomic and metabolomic data to describe the genes involved in cellulose degradation and to provide hypotheses for the biofuel production pathways. In total, almost 80 biosynthetic clusters were identified, including several previously found only in plants. Additionally, many transcriptionally active regions outside of genes showed condition-specific expression, offering more evidence for the role of long non-coding RNA in gene regulation. This is one of the highest quality fungal genomes and, to our knowledge, the only thoroughly annotated and transcriptionally profiled fungal endophyte genome currently available. The analyses and datasets contribute to the study of cellulose degradation and biofuel production and provide the genomic foundation for the study of a model endophyte system