Total synthesis of (+/-)-aspirochlorine, The

1993 Fall.Includes bibliographical references.Aspirochlorine is a unique epidithiodioxopiperazine isolated from Aspergillus oryzae, Asp. tamarii and Asp. flavus. The molecule contains a highly unusual bicyclo [3.2.2]disulfide ring system which has previously never been prepared. The first total synthesis of (±)-Aspirochlorine was achieved from commercially available 5-chlororesorcinol 324 in 16 steps. The key step in the synthesis was an efficient intramolecular cycloaddition reaction of hydroxamic ester 344 to form the parent spiro [benzofuran-2(3H),2'-piperazine] ring system 345 as a single stereoisomer. In addition the synthesis employed a 2-nitrobenzyl moiety as a novel amide protecting group. The 2-nitrobenzyl group could be removed in 72% yield under photolytic conditions. Synthetic aspirochlorine was identical to natural material in comparison by 1H NMR, IR and HPLC. Comparison of the biological activity of aspirochlorine versus other epidithiodioxopiperazines was investigated as a function of superoxide production. Although aspirochlorine was shown to be capable of producing superoxide as evidenced in DNA plasmid nicking and NBT reduction assays, the observed activity was less than the 6-membered epidithiodioxopiperazines

Solid state 13C NMR analysis of shales and coals from Laramide Basins. Final report, March 1, 1995--March 31, 1996

This Western Research Institute (WRI) jointly sponsored research (JSR) project augmented and complemented research conducted by the University of Wyoming Institute For Energy Research for the Gas Research Institute. The project, {open_quotes}A New Innovative Exploitation Strategy for Gas Accumulations Within Pressure Compartments,{close_quotes} was a continuation of a project funded by the GRI Pressure Compartmentalization Program that began in 1990. That project, {open_quotes}Analysis of Pressure Chambers and Seals in the Powder River Basin, Wyoming and Montana,{close_quotes} characterized a new class of hydrocarbon traps, the discovery of which can provide an impetus to revitalize the domestic petroleum industry. In support of the UW Institute For Energy Research`s program on pressure compartmentalization, solid-state {sup 13}C NMR measurements were made on sets of shales and coals from different Laramide basins in North America. NMR measurements were made on samples taken from different formations and depths of burial in the Alberta, Bighorn, Denver, San Juan, Washakie, and Wind River basins. The carbon aromaticity determined by NMR was shown to increase with depth of burial and increased maturation. In general, the NMR data were in agreement with other maturational indicators, such as vitrinite reflectance, illite/smectite ratio, and production indices. NMR measurements were also obtained on residues from hydrous pyrolysis experiments on Almond and Lance Formation coals from the Washakie Basin. These data were used in conjunction with mass and elemental balance data to obtain information about the extent of carbon aromatization that occurs during artificial maturation. The data indicated that 41 and 50% of the original aliphatic carbon in the Almond and Lance coals, respectively, aromatized during hydrous pyrolysis

RESIDUA UPGRADING EFFICIENCY IMPROVEMENT MODELS: WRI COKING INDEXES

Pyrolysis experiments were conducted with three residua at 400 C (752 F) at various residence times. The wt % coke and gaseous products were measured for the product oils. The Western Research Institute (WRI) Coking Indexes were determined for the product oils. Measurements were made using techniques that might correlate with the Coking Indexes. These included spin-echo proton nuclear magnetic resonance spectroscopy, heat capacity measurements at 280 C (536 F), and ultrasonic attenuation. The two immiscible liquid phases that form once coke formation begins were isolated and characterized for a Boscan residuum pyrolyzed at 400 C (752 F) for 55 minutes. These materials were analyzed for elemental composition (CHNS), porphyrins, and metals (Ni,V) content

Evaluation of the Effect of Hydrated Lime on the Scavenging of Feral Swine (\u3ci\u3eSus Scrofa\u3c/i\u3e) Carcasses and Implications for Managing Carcass-Based Transmission of African Swine Fever Virus

African swine fever (ASF) is a devastating hemorrhagic disease marked by extensive morbidity and mortality in infected swine. The recent global movement of African swine fever virus (ASFV) in domestic and wild swine (Sus scrofa) populations has initiated preparedness and response planning activities within many ASF-free countries. Within the US, feral swine are of utmost concern because they are susceptible to infection, are wide-spread, and are known to interact with domestic swine populations. African swine fever virus is particularly hardy and can remain viable in contaminated carcasses for weeks to months; therefore, carcass-based transmission plays an important role in the epidemiology of ASF. Proper disposal of ASF-infected carcasses has been demonstrated to be paramount to curbing an ASF outbreak in wild boar in Europe; preparedness efforts in the US anticipate carcass management being an essential component of control if an introduction were to occur. Due to environmental conditions, geographic features, or limited personnel, immediately removing every carcass from the landscape may not be viable. Hydrated lime converts to calcium carbonate, forming a sterile crust that may be used to minimize pathogen amplification. Any disturbance by scavenging animals to the sterile crust would nullify the effect of the hydrated lime; therefore, this pilot project aimed to evaluate the behavior of scavenging animals relative to hydrated lime-covered feral swine carcasses on the landscape. At two of the three study sites, hydrated limetreated carcasses were scavenged less frequently compared to the control carcasses. Additionally, the median time to scavenging was 1 d and 6 d for control versus hydrated lime-treated carcasses, respectively. While results of this study are preliminary, hydrated lime may be used to deter carcass disruption via scavenging in the event that the carcass cannot be immediately removed from the landscape

Transformations in organic sulfur speciation during maturation of Monterey shale: Constraints from laboratory experiments

A series of hydrous pyrolysis experiments were conducted at temperatures ranging from 125 to 360C at 350 bars pressure to examine variations in sulfur speciation during thermal maturation of Monterey shale. The total sediment, kerogen and bitumen from each experiment in addition to unheated representatives were analyzed via x-ray absorption spectroscopy, pyrolysis-gas chromatography, {sup 30}NMR spectrometry, elemental analysis, thin-layer chromatography and reflected light microscopy. Based on these measurements, it was possible to recognize three distinct temperature regimes, within which the type and amount of sulfur in the analyzed fractions underwent transformations: (1) between 150 and 225C significant proportion of kerogen-bound sulfur is lost probably due to the collapse of polysulfide bridges; (2) between 225 and 275C, cleavage of -S-S- and -S-C- linkages within the kerogen is believed to occur, resulting in substantial production of polar sulfur-rich bitumen; (3) above 275C total bitumen yields as well as the proportion of bitumen sulfur decrease, while C-C bond scission leads to increased yields of saturated and aromatic hydrocarbons. The results from this study clearly and quantitatively establish a link between organically-bound sulfur, and more specifically, organic polysulfides, and the low-temperature evolution of soluble petroleum-like products (bitumen) from sulfur-rich source rocks

A transient homotypic interaction model for the influenza A virus NS1 protein effector domain

Influenza A virus NS1 protein is a multifunctional virulence factor consisting of an RNA binding domain (RBD), a short linker, an effector domain (ED), and a C-terminal 'tail'. Although poorly understood, NS1 multimerization may autoregulate its actions. While RBD dimerization seems functionally conserved, two possible apo ED dimers have been proposed (helix-helix and strand-strand). Here, we analyze all available RBD, ED, and full-length NS1 structures, including four novel crystal structures obtained using EDs from divergent human and avian viruses, as well as two forms of a monomeric ED mutant. The data reveal the helix-helix interface as the only strictly conserved ED homodimeric contact. Furthermore, a mutant NS1 unable to form the helix-helix dimer is compromised in its ability to bind dsRNA efficiently, implying that ED multimerization influences RBD activity. Our bioinformatical work also suggests that the helix-helix interface is variable and transient, thereby allowing two ED monomers to twist relative to one another and possibly separate. In this regard, we found a mAb that recognizes NS1 via a residue completely buried within the ED helix-helix interface, and which may help highlight potential different conformational populations of NS1 (putatively termed 'helix-closed' and 'helix-open') in virus-infected cells. 'Helix-closed' conformations appear to enhance dsRNA binding, and 'helix-open' conformations allow otherwise inaccessible interactions with host factors. Our data support a new model of NS1 regulation in which the RBD remains dimeric throughout infection, while the ED switches between several quaternary states in order to expand its functional space. Such a concept may be applicable to other small multifunctional proteins