Structural Characteristics and Reactivity Relationships of Nitroaromatic and Nitramine Explosives – A Review of Our Computational Chemistry and Spectroscopic Research

Although much has been discovered, discussed and written as to problems of contamination by various military unique compounds, particularly by the nitrogen based energetics (NOCs), remaining problems dictate further evaluation of actual and potential risk to the environment by these energetics and their derivatives and metabolites through determination of their environmental impact—transport, fate and toxicity. This work comprises an effort to understand structural relationships and degradation mechanisms of current and emerging explosives, including nitroaromatic; cyclic and cage cyclic nitramine; and a nitrocubane. This review of our computational chemistry and spectroscopic research describes and compares competitive degradation mechanisms by free radical oxidative, reductive and alkali hydrolysis, relating them, when possible, to environmental risk.     

A fluidized bed retort for oil sands

Fluid bed retorting of oil sands is a viable method of extracting oil from mined oil sands. The process is based on a direct heating concept in which one vessel is utilized for the pyrolysis and vaporization of the bitumen contained in the oil sand and for the burning of the residuals which remain with the sand. Experimental results show that a significantly upgraded liquid hydrocarbon product can be obtained. Oil yields can exceed eighty per cent of the bitumen present in the feed material. The sulfur content of the produced oil is reduced. Gas produced can have a significant heating value and contains sulfur mainly in the form of hydrogen sulfide. Refluxing of the overhead product increases liquid yields and reduces the sulfur content of the oil. Water injection and the use of enriched air has a beneficial effect on the process. Thermal efficiencies in excess of eighty per cent can be achieved without recovering the heat from the expended sand.     

Coupled Biosynthesis of Volatiles and Salinosporamide A in Salinispora tropica

Terrestrial bacteria, especially actinomycetes, are known to be prolific producers of volatile compounds. We show here that bacteria from ocean sediments can also release complex bouquets of volatiles. The actinomycete Salinispora tropica produces cyclohexenyl compounds not previously known in nature, such as methyl cyclohex‐2‐ene‐1‐carboxylate ( 9 ), methyl 2‐(cyclohex‐2‐en‐1‐yl)acetate ( 10 ), methyl (E/Z)‐2‐(cyclohex‐2‐en‐1‐ylidene)acetate ( 11 / 12 ), and related alcohols 8 and 13 . These compounds were identified by GC/MS and confirmed by synthesis. In addition, rare spiroacetals, aromatic compounds, short‐chain acids and esters, alcohols, and various cyclic compounds were produced by the bacteria. The biosynthesis of the cyclohexenyl compounds is closely coupled to that of cyclohexenylalanine ( 4 ), a building block of salinosporamide A, a proteasome inhibitor produced by S. tropica. Analysis of S. tropica strains that harbor knockouts of the salinosporamide biosynthetic genes salX and salD, coupled with feeding experiments, revealed that 3‐(cyclohex‐2‐en‐1‐yl)‐2‐oxopropanoic acid ( 60 ) and 3‐(cyclohex‐2‐en‐1‐ylidene)‐2‐oxopropanoic acid (isomers 61 and 62 ) are important intermediates in the biosynthesis of salinosporamide A, 4 , and 8 – 13 .     

Synthetic Phosphoethanolamine Cellobiose Promotes Escherichia coli Biofilm Formation and Congo Red Binding

Urinary tract infections (UTIs) are caused by bacteria growing in complex, multicellular enclosed aggregates known as biofilms. Recently, a zwitterionic cellulose derivative produced in Escherichia coli (E. coli) was determined to play an important role in the formation and assembly of biofilms. In order to produce a minimal, yet structurally defined tool compound to probe the biology of the naturally occurring polymer, we have synthesized a zwitterionic phosphoethanolamine cellobiose (pEtN cellobiose) and evaluated its biofilm activity in the Gram-negative bacterium E. coli, a pathogen implicated in the pathogenesis of UTIs. The impact of synthetic pEtN cellobiose on biofilm formation was examined via colorimetric assays which revealed an increase in cellular adhesion to an abiotic substrate compared to untreated samples. Additionally, Congo red binding assays indicate that culturing E. coli in the presence of pEtN cellobiose enhances Congo Red binding to bacterial cells. These results reveal new opportunities to study the impact glycopolymers have on cellular adhesion in Gram-negative pathogens.     

The South African and Namibian Populations of the Resurrection Plant <Emphasis Type="Italic">Myrothamnus flabellifolius</Emphasis> are Genetically Distinct and Display Variation in Their Galloylquinic Acid Composition

The polyphenol contents and compositions in desiccated leaves of Myrothamnus flabellifolius plants collected in various locations in Namibia and South Africa were analyzed using UV spectroscopy and high-performance liquid chromatography–mass spectrometry. A study of the genetic relatedness of these populations was also performed by determination of the DNA sequence of the intergenic spacer region between the psbA and the trnH genes in the chloroplast genome. Namibian M. flabellifolius plants contained significantly more polyphenols than South African plants. Namibian plants essentially contained a single polyphenol, 3,4,5-tri-O-galloylquinic acid, whereas South African plants contained a variety of galloylquinic acids including 3,4,5-tri-O-galloylquinic acid together with higher molecular weight galloylquinic acids. Sequence analysis revealed a 1.4% divergence between Namibian and South African plants corresponding to the separation of these populations of approximately 4 × 10⁶ years. The significance of the poly-phenol content and composition to the desiccation tolerance of the two popu-lations is discussed.     

The Measurement of Ambient Bioaerosol Exposure

Monitoring of ambient bioaerosol concentrations through the characterization of outdoor particulate matter (PM) has only been performed on a limited basis in North Carolina (NC) and was the goal of this research. Ambient samples of PM _2.5 (fine) and PM _10?2.5 (coarse) were collected for a six-month period and analyzed for mold, endotoxins and protein. PM _2.5 and PM _10?2.5 concentrations of these bioaerosols were reported as a function of PM mass, as well as volume of air sampled. The mass of PM _2.5 was almost twice that of the PM _10?2.5 ; however, the protein and endotoxin masses were greater in the coarse than the fine PM indicating an enrichment in the coarse PM. The protein and mold results demonstrated a seasonal pattern, both being higher in the summer than in the winter. Except for an occasional excursion, the endotoxin data remained fairly constant throughout the six months of the study.     

Intra-Community Variability in Total Particle Number Concentrations in the San Pedro Harbor Area (Los Angeles,California)

Recent evidence links elevated ultrafine particle (UFP) concentrations with adverse health effects, but exposure assessments based upon PM _2.5 mass concentrations may be misleading. In order to better understand and quantify intra-community variability in UFP concentrations, a dense network of 14 monitoring sites was set-up in Los Angeles in two clusters—San Pedro/Wilmington and West Long Beach—in communities surrounding the Ports of Los Angeles and Long Beach. The network measured total particle number concentrations greater than 7 nm in diameter. In this range, UFP comprise approximately 90% of the total. Port-related activities—particularly goods movement associated with high volumes of heavy-duty diesel vehicle (HDDV) traffic—represent significant UFP sources. The field study was conducted from mid-February through mid-December 2007 to assess diurnal, seasonal, and spatial patterns and intra-community variability in total particle number concentrations. For sites within a few km of each other, simultaneous particle number concentrations can vary up to a factor of 10 (< 10,000 cm^?3 up to 90,000 cm^?3 for hourly averages calculated by month). The median hourly correlation coefficient (r) across all sites was modest and varied from 0.3 to 0.56. Specific site locations, particularly proximity to roadways used for goods movement, strongly affect observations. Clear diurnal and seasonal patterns are evident in the data. A diurnal pattern associated with high HDDV volumes and goods movement was identified. Coefficients of Divergence calculated for the site pairs suggest moderate heterogeneity overall (median study COD ≈ 0.35). The intra-urban variability observed in this study is comparable to and exceeds the inter-urban variability observed in a previous study in Los Angeles. UFP concentrations can vary considerably on short spatial scales in source-rich environments strongly influencing the accuracy of exposure assessments.     

Bioactivity‐Guided Genome Mining Reveals the Lomaiviticin Biosynthetic Gene Cluster in Salinispora tropica

The use of genome sequences has become routine in guiding the discovery and identification of microbial natural products and their biosynthetic pathways. In silico prediction of molecular features, such as metabolic building blocks, physico‐chemical properties or biological functions, from orphan gene clusters has opened up the characterization of many new chemo‐ and genotypes in genome mining approaches. Here, we guided our genome mining of two predicted enediyne pathways in Salinispora tropica CNB‐440 by a DNA interference bioassay to isolate DNA‐targeting enediyne polyketides. An organic extract of S. tropica showed DNA‐interference activity that surprisingly was not abolished in genetic mutants of the targeted enediyne pathways, ST_pks1 and spo. Instead we showed that the product of the orphan type II polyketide synthase pathway, ST_pks2, is solely responsible for the DNA‐interfering activity of the parent strain. Subsequent comparative metabolic profiling revealed the lomaiviticins, glycosylated diazofluorene polyketides, as the ST_pks2 products. This study marks the first report of the 59 open reading frame lomaiviticin gene cluster (lom) and supports the biochemical logic of their dimeric construction through a pathway related to the kinamycin monomer.     

Discovery and Biosynthesis of Ureidopeptide Natural Products Macrocyclized via Indole N-acylation in Marine Microbulbifer spp. Bacteria

Commensal bacteria associated with marine invertebrates are underappreciated sources of chemically novel natural products. Using mass spectrometry, we had previously detected the presence of peptidic natural products in obligate marine bacteria of the genus Microbulbifer cultured from marine sponges. In this report, the isolation and structural characterization of a panel of ureidohexapeptide natural products, termed the bulbiferamides, from Microbulbifer strains is reported wherein the tryptophan side chain indole participates in a macrocyclizing peptide bond formation. Genome sequencing identifies biosynthetic gene clusters encoding production of the bulbiferamides and implicates the involvement of a thioesterase in the indolic macrocycle formation. The structural diversity and widespread presence of bulbiferamides in commensal microbiomes of marine invertebrates point toward a possible ecological role for these natural products.     

Stability and kinetics of iron-terephthalate MOFs with diverse structures in aqueous pollutant degradation

Synthesized iron-terephthalate metal–organic frameworks (MOFs), MIL-101 and MOF-235, with contrasting morphologies are examined to elucidate the role of structural arrangement in catalytic aqueous pollutant degradation. MIL-101 demonstrates a larger pseudo-first order rate constant than MOF-235 (3.5 ± 0.2 mol_Fe⁻¹ · s⁻¹ vs. 0.84 ± 0.07 mol_Fe⁻¹ · s⁻¹) toward oxidation of methylene blue (MB) dye with excess hydrogen peroxide at ambient temperature, likely due to intrinsic differences in ligand coordination at their metal nodes. However, despite continued activity upon reuse, both MOFs undergo structural alterations resulting in formation of leached species active for MB degradation that have been obfuscated in previous studies. Detailed stability testing and ex situ characterization of recovered catalyst, examinations that remain underreported in Fe-MOF studies for pollutant oxidation, indicate that water plays a prominent role in the breakdown of these frameworks. Collectively, this work informs the interpretation and use of common Fe-MOFs for aqueous applications, relating material changes to observed reaction phenomena.