Lymphotoxins and cytomegalovirus cooperatively induce interferon-beta, establishing host-virus détente

Tumor necrosis factor (TNF)-related cytokines regulate cell death and survival and provide strong selective pressures for viruses, such as cytomegalovirus (CMV), to evolve counterstrategies in order to persist in immune-competent hosts. Signaling by the lymphotoxin (LT)-β receptor or TNF receptor-1, but not Fas or TRAIL receptors, inhibits the cytopathicity and replication of human CMV by a nonapoptotic, reversible process that requires nuclear factor κB (NF-κB)-dependent induction of interferon-β (IFN-β). Efficient induction of IFN-β requires virus infection and LT signaling, demonstrating the need for both host and viral factors in the curtailment of viral replication without cellular elimination. LTα-deficient mice and LTβR-Fc transgenic mice were profoundly susceptible to murine CMV infection. Together, these results reveal an essential and conserved role for LTs in establishing host defense to CMV

Pyrolysis of coal model compounds containing aromatic carboxylic acids: The role of carboxylic acids in cross-linking reactions in low-rank coal

The pyrolysis of 1-(3-carboxyphenyl)-2(4-biphenyl)ethane (1) diluted in 10-fold excess of naphthalene has been studied at 400 {degrees}C to investigate whether decarboxylation of aromatic carboxylic acids can lead to cross-linked products. The dominant mechanism for decarboxylation was found to be an acid-promoted ionic pathway that does not lead to cross-linking. However, a small amount of cross-linked products (i.e. naphthalene grafted onto decarboxylated 1) were formed. The yields of the cross-linked products were found to be decreased in the presence of a hydrogen donor solvent, tetralin, suggesting that these products were formed by a free-radical pathway. The mechanism for the formation of cross-linked products was proposed to occur from the formation and decomposition of anhydrides of 1 during pyrolysis

Investigation of the role of aromatic carboxylic acids in cross-linking processes in low-rank coals

In the pyrolysis and liquefaction of low-rank coals, low-temperature cross-linking reactions have been correlated with the loss of carboxyl groups and the evolution of CO{sub 2} and H{sub 2}O. It is not clearly understood how decarboxylation leads to cross-linking beyond the suggestion that decarboxylation could be a radical process that involves radical recombination or radical addition reactions. We have recently conducted a study of the pyrolysis of 1,2-(3,3{prime}-dicarboxyphenyl)ethane (1) and 1,2-(4,4{prime}-dicarboxyphenyl)ethane (2) and found that decarboxylation occurs readily between 350-425 {degrees}C with no evidence of coupling products or products representative of cross-links. We proposed that decarboxylation occurred primarily by an acid-promoted cationic pathway, and the source of acid was a second carboxylic acid. The decarboxylation of 1 and 2 was investigated in diphenyl ether and naphthalene as inert diluents. In each solvent, the rate of decarboxylation dropped by roughly a factor of 2 upon dilution from the neat liquid to ca. 0.4 mole fraction of acid, but further dilution had no effect on the rate. This could be a consequence of hydrogen bonding or an intramolecular protonation. Molecular mechanics calculations indicated that 1 and 2 can adopt an appropriate conformation for internal proton transfer from a carboxy group on one ring to the second aryl ring without a significant energy penalty. In addition, the dicarboxylic acid could internally hydrogen bond, which may further complicate the reaction mechanism. Therefore, we have conducted a study of the pyrolysis of a monocarboxybibenzyl, 1-(3-carboxyphenyl)-2-(4-biphenyl)ethane (3), to determine if decarboxylation occurs by an ionic pathway in the absence of intramolecular pathways

Systematics of Fission Barriers in Superheavy Elements

We investigate the systematics of fission barriers in superheavy elements in the range Z = 108-120 and N = 166-182. Results from two self-consistent models for nuclear structure, the relativistic mean-field (RMF) model as well as the non-relativistic Skyrme-Hartree-Fock approach are compared and discussed. We restrict ourselves to axially symmetric shapes, which provides an upper bound on static fission barriers. We benchmark the predictive power of the models examining the barriers and fission isomers of selected heavy actinide nuclei for which data are available. For both actinides and superheavy nuclei, the RMF model systematically predicts lower barriers than most Skyrme interactions. In particular the fission isomers are predicted too low by the RMF, which casts some doubt on recent predictions about superdeformed ground states of some superheavy nuclei. For the superheavy nuclei under investigation, fission barriers drop to small values around Z = 110, N = 180 and increase again for heavier systems. For most of the forces, there is no fission isomer for superheavy nuclei, as superdeformed states are in most cases found to be unstable with respect to octupole distortions.Comment: 17 pages REVTEX, 12 embedded eps figures. corrected abstrac

Contrasting retrogressive rearrangement pathways during thermolysis of silica-immobilized benzyl phenyl ether

Many coal model compound studies have focused on the mechanisms of bond cleavage reactions, and the means to alter reaction conditions to promote such reactions. However, there has become increasing interest in elucidating mechanisms associated with retrogressive or retrograde reactions in coal processing, which involve the formation of refractory bonds. Retrograde reactions inhibit efficient thermochemical processing of coals into liquid fuels, which has been particularly well-documented for low rank coals where abundant oxygen-containing functional groups are thought to play a key role in the chemistry. Much less is known about retrogressive reactions for ether-containing model compounds. Radical recombination through ring coupling of phenoxy radicals in benzyl phenyl ether (BPE) is known to lead to more refractory diphenylmethane linkages to a limited extent. Since this chemistry may be attributed at least in part to cage recombination, it could be promoted in a diffusionally constrained environment such as in the coal macromolecule. Using silica-immobilization to simulate restricted diffusion in coal, the authors have found that retrogressive reactions can be promoted for certain hydrocarbon model compounds. The authors have now begun an examination of the thermolysis behavior of silica-immobilized benzyl phenyl ether at 275--325 C. The initial results indicate that two retrogressive reaction pathways, radical recombination and molecular rearrangement through Si-O-C linkage to the surface of PhOCH{center_dot}Ph, are promoted by restricted diffusion. Remarkably, the retrograde products typically account for 50 mol% of the thermolysis products

Flash vacuum pyrolysis of lignin model compounds

Despite the extensive research into the pyrolysis of lignin, the underlying chemical reactions that lead to product formation are poorly understood. Detailed mechanistic studies on the pyrolysis of biomass and lignin under conditions relevant to current process conditions could provide insight into utilizing this renewable resource for the production of chemicals and fuel. Currently, flash or fast pyrolysis is the most promising process to maximize the yields of liquid products (up to 80 wt %) from biomass by rapidly heating the substrate to moderate temperatures, typically 500{degrees}C, for short residence times, typically less than two seconds. To provide mechanistic insight into the primary reaction pathways under process relevant conditions, we are investigating the flash vacuum pyrolysis (FVP) of lignin model compounds that contain a {beta}-ether. linkage and {alpha}- or {gamma}-alcohol, which are key structural elements in lignin. The dominant products from the FVP of PhCH{sub 2}CH{sub 2}OPh (PPE), PhC(OH)HCH{sub 2}OPh, and PhCH{sub 2}CH(CH{sub 2}OH)OPh at 500{degrees}C can be attributed to homolysis of the weakest bond in the molecule (C-O bond) or 1,2-elimination. Surprisingly, the hydroxy-substituent dramatically increases the decomposition of PPE. It is proposed that internal hydrogen bonding is accelerating the reaction

Flash Vacuum Pyrolysis of Lignin Model Compounds: Reaction Pathways of Aromatic Methoxy Groups

Currently, there is interest in utilizing lignin, a major constituent of biomass, as a renewable source of chemicals and fuels. High yields of liquid products can be obtained from the flash or fast pyrolysis of biomass, but the reaction pathways that lead to product formation are not understood. To provide insight into the primary reaction pathways under process relevant conditions, we are investigating the flash vacuum pyrolysis (FVP) of lignin model compounds at 500 C. This presentation will focus on the FVP of {beta}-ether linkages containing aromatic methoxy groups and the reaction pathways of methoxy-substituted phenoxy radicals

Thermolysis of a polymer model of aromatic carboxylic acids in low-rank coal

To compliment our current investigation into the role that decarboxylation of aromatic carboxylic acids plays in the low-temperature cross-linking of low-rank coals, we are investigating the thermolysis of a polymeric coal model compound to determine if the polymeric network structure of coal can alter the decarboxylation pathways. In this investigation, a bibenzylic polymer, poly-(m-xylylene-co-5-carboxy-m-xylylene), 1, was synthesized containing 2.3 carboxylic acids per 100 carbons, which is similar to that found in Zapp lignite. The pyrolysis of 1 was compared to poly-m-xylylene, 2, and the methyl ester of 1, 3, to determine if the carboxy group enhances cross-linking reactions. The major product from the pyrolysis of 1 at 375{degrees} C or 400{degrees} C for 1 h was a THF insoluble residue (60-75 wt%), while pyrolysis of 2 or the methyl ester of 1 produced only a THF soluble product. The mechanistic pathways leading to cross-linking will be discussed

Review: Perspective on high-performing dairy cows and herds

Milk and dairy products provide highly sustainable concentrations of essential amino acids and other required nutrients for humans; however, amount of milk currently produced per dairy cow globally is inadequate to meet future needs. Higher performing dairy cows and herds produce more milk with less environmental impact per kg than lower performing cows and herds. In 2018, 15.4% of the world\u27s dairy cows produced 45.4% of the world\u27s dairy cow milk, reflecting the global contribution of high-performing cows and herds. In high-performing herds, genomic evaluations are utilized for multiple trait selection, welfare is monitored by remote sensing, rations are formulated at micronutrient levels, health care is focused on prevention and reproduction is managed with precision. Higher performing herds require more inputs and generate more waste products per cow, thus innovations in environmental management on such farms are essential for lowering environmental impacts. Our focus is to provide perspectives on technologies and practices that contribute most to sustainable production of milk from high-performing dairy cows and herds

Mechanistic Investigation into the Decarboxylation of Aromatic Carboxylic Acids

It has been proposed that carboxylic acids and carboxylates are major contributors to cross-linking reactions in low-rank coals and inhibit its thermochemical processing. Therefore, the thermolysis of aromatic carboxylic acids was investigated to determine the mechanisms of decarboxylation at temperatures relevant to coal processing, and to determine if decarboxylation leads to cross-linking (i.e., formation of more refractory products). From the thcrmolysis of simple and polymeric coal model compounds containing aromatic carboxylic acids at 250-425 �C, decarboxylation was found to occur primarily by an acid promoted ionic pathway. Carboxylate salts were found to enhance the decarboxylation rate, which is consistent with the proposed cationic mechanism. Thermolysis of the acid in an aromatic solvent, such as naphthalene, produced a small amount of arylated products (~5 mol%)), which constitute a low-temperature cross-link. These arylated products were formed by the rapid decomposition of aromatic anhydrides, which are in equilibrium with the acid. These anhydrides decompose by a free radical induced decomposition pathway to form atyl radicals that can add to aromatic rings to form cross-links or abstract hydrogen. Large amounts of CO were formed in the thennolysis of the anhydrides which is consistent with the induced decomposition pathway. CO was also formed in the thermolysis of the carboxylic acids in aromatic solvents which is consistent with the formation and decomposition of the anhydride. The formation of anhydride linkages and cross-links was found to be very sensitive to the reactions conditions. Hydrogen donor solvents, such as tetralin, and water were found to decrease the formation of arylated products. Silar reaction pathways were also found in the thermolysis of a polymeric model that contained aromatic carboxylic acids. In this case, anhydride formation and decomposition produced an insoluble polymer, while the O-methylated polymer and the non-carboxylated polymer produced a soluble thermolysis product