Sulfur-tolerant NOx storage traps: an infrared and thermodynamic study of the reactions of alkali and alkaline-earth metal sulfates

The sulfur tolerance of a barium-containing NOx storage/reduction trap was investigated using infrared analysis. It was confirmed that barium carbonate could be replaced by barium sulfate by reaction with low concentrations of sulfur dioxide (50 ppm) in the presence of large concentrations of carbon dioxide (10%) at temperatures up to 700 degreesC. These sulfates could at least be partially removed by switching to hydrogen-rich conditions at elevated temperatures. Thermodynamic calculations were used to evaluate the effects of gas composition and temperature on the various reactions of barium sulfate and carbonate under oxidizing and reducing conditions. These calculations clearly showed that if, under a hydrogen-rich atmosphere, carbon dioxide is included as a reactant and barium carbonate as a product then barium sulfate can be removed by reaction with carbon dioxide at a much lower temperature than is possible by decomposition to barium oxide. It was also found that if hydrogen sulfide was included as a product of decomposition of barium sulfate instead of sulfur dioxide then the temperature of reaction could be significantly lowered. Similar calculations were conducted using a selection of other alkaline-earth and alkali metals. In this case calculations were simulated in a gas mixture containing carbon monoxide, hydrogen and carbon dioxide with partial pressures similar to those encountered in real exhausts during switches to rich conditions. The results indicated that there are metals such as lithium and strontium with less stable sulfates than barium, which may also possess sufficient NOx storage capacity to give sulfur-tolerant NOx traps.

Palladium-catalyzed liquid-phase hydrogenation/hydrogenolysis of disulfides

For the first time, the hydrogenation/hydrogenolysis of a range of disulfides has been achieved over a supported palladium catalyst using hydrogen under relatively benign conditions. These unexpected results demonstrate that it is possible to avoid the poisoning of the catalyst by either the nitrogen-containing groups or the sulfur species, allowing both efficient reaction and recycling of the catalyst under the proper conditions (e.g., at low temperatures). A slight loss in activity was found on recycling; however, the catalyst activity can be recovered using hydrogen pretreatment. The reaction mechanism for the hydrogenolysis and hydrogenation of ortho-, meta-, and para-dinitrodiphenyldisulfide to the corresponding aminothiophenol has been elucidated. Density functional theory calculations were used to investigate the adsorption mode of the dinitrodiphenyldisulfides; a clear dependence on adsorption geometry was found regarding whether the molecule is cleaved at the S-S bond before the reduction of the nitro group or vice versa. This study demonstrates the versatility of these catalysts for the hydrogenation/hydrogenolysis of sulfur-containing molecules, which normally are considered poisons, and will extend their use to a new family of substrates. (C) 2007 Elsevier Inc. All rights reserved.

First-in-Class Inhibitors of Sulfur Metabolism with Bactericidal Activity against Non-Replicating M-tuberculosis

Development of effective therapies to eradicate persistent, slowly replicating M. tuberculosis (Mtb) represents a significant challenge to controlling the global TB epidemic. To develop such therapies, it is imperative to translate information from metabolome and proteome adaptations of persistent Mtb into the drug discovery screening platforms. To this end, reductive sulfur metabolism is genetically and pharmacologically implicated in survival, pathogenesis, and redox homeostasis of persistent Mtb. Therefore, inhibitors of this pathway are expected to serve as powerful tools in its preclinical and clinical validation as a therapeutic target for eradicating persisters. Here, we establish a first functional HTS platform for identification of APS reductase (APSR) inhibitors, a critical enzyme in the assimilation of sulfate for the biosynthesis of cysteine and other essential sulfur-containing molecules. Our HTS campaign involving 38?350 compounds led to the discovery of three distinct structural classes of APSR inhibitors. A class of bioactive compounds with known pharmacology displayed potent bactericidal activity in wild-type Mtb as well as MDR and XDR clinical isolates. Top compounds showed markedly diminished potency in a conditional Delta APSR mutant, which could be restored by complementation with Mtb APSR. Furthermore, ITC studies on representative compounds provided evidence for direct engagement of the APSR target. Finally, potent APSR inhibitors significantly decreased the cellular levels of key reduced sulfur-containing metabolites and also induced an oxidative shift in mycothiol redox potential of live Mtb, thus providing functional validation of our screening data. In summary, we have identified first-in-class inhibitors of APSR that can serve as molecular probes in unraveling the links between Mtb persistence, antibiotic tolerance, and sulfate assimilation, in addition to their potential therapeutic value.

Controlling the Sulfur Poisoning of Ag/Al2O3 Catalysts for the Hydrocarbon SCR Reaction by Using a Regenerable SOx Trap

The deactivation of a silver-based hydrocarbon selective catalytic reduction catalyst by SOx and the subsequent regeneration under various operating conditions has been investigated. Using a sulfur trap based on a silica-supported catalyst it was found that, for a Ag/SiO2 + Ag/Al2O3 combination, the negative effect of SO2 on the n-octane-SCR reaction can be eliminated under normal operating conditions. The trap can be regenerated by hydrogen at low temperatures or at higher temperatures using a hydrocarbon reductant.

Chemical functionalities of high and low sulfur Australian coals : a case study using micro attenuated total reflectance–fourier transform infrared (ATR–FTIR) spectrometry

The macerals in bituminous coals with varying organic sulfur content from the Early Permian Greta Coal Measures at three locations (Southland Colliery, Drayton Colliery and the Cranky Corner Basin), in and around the Sydney Basin (Australia), have been studied using light-element electron microprobe (EMP) analysis and micro-ATR–FTIR. Electron microprobe analysis of individual macerals reveals that the vitrinite in both the Cranky Corner Basin and Drayton Colliery (Puxtrees seam) samples have similar carbon contents (ca. 78% C in telocollinite), suggesting that they are of equivalent rank. However, the Cranky Corner coals have anomalously low vitrinite reflectance (down to 0.45%) vs. the Drayton materials (ca. 0.7%). They also have very high organic S content (3–6.5%) and lower O content (ca. 10%) than the equivalent macerals in the Drayton sample (0.7% S and 15.6% O). A study was carried out to investigate the impacts of the high organic S on the functional groups of the macerals in these two otherwise iso-rank, stratigraphically-equivalent seams. An iso-rank low-S coal from the overlying Wittingham Coal Measures near Muswellbrook and coals of slightly higher rank from the Greta Coal Measures at Southland Colliery near Cessnock were also evaluated using the same techniques to extend the data set. Although the telocollinite in the Drayton and Cranky Corner coals have very similar carbon content (ca.78% C), the ATR–FTIR spectra of the vitrinite and inertinite macerals in these respectively low S and high S coals show some distinct differences in IR absorbance from various aliphatic and aromatic functional groups. The differences in absorbance of the aliphatic stretching bands (2800–3000 cm−1) and the aromatic carbon (CC) peak at 1606 cm−1 are very obvious. Compared to that of the Drayton sample (0.7% S and 15% O), the telocollinite of the Cranky Corner coal (6% S and 10% O) clearly shows: (i) less absorbance from OH groups, represented by a broad region around 3553 cm−1, (ii) much stronger aliphatic C–H absorbance (stretching modes around 3000–2800 cm−1 and bending modes around 1442 cm−1) and (iii) less absorbance from aromatic carbon functional groups (peaking at 1606 cm−1). Evaluation of the iso-rank Drayton and Cranky Corner coals shows that: (i) the aliphatic C–H absorbances decrease with increasing oxygen content but increase with increasing organic S content and (ii) the aromatic H to aliphatic H ratio (Har/Hali) for the telocollinite increases with (organic) O%, but decreases progressively with increasing organic S. The high organic S content in the maceral appears to be accompanied by a greater proportion of aliphatic functional groups, possibly as a result of some of the O within maceral ring structures in the high S coal samples being replaced.

Genetic Analysis of Tolerance to Rice Tungro Bacilliform Virus in Rice (Oryza sativa L.) Through Agroinoculation

Balimau Putih [an Indonesian cultivar tolerant to rice tungro bacilliform virus (RTBV)] was crossed with IR64 (RTBV, susceptible variety) to produce the three filial generations F1, F2 and F3. Agroinoculation was used to introduce RTBV into the test plants. RTBV tolerance was based on the RTBV level in plants by analysis of coat protein using enzyme-linked immunosorbent assay. The level of RTBV in cv. Balimau Putih was significantly lower than that of IR64 and the susceptible control, Taichung Native 1. Mean RTBV levels of the F1, F2 and F3 populations were comparable with one another and with the average of the parents. Results indicate that there was no dominance and an additive gene action may control the expression of tolerance to RTBV. Tolerance based on the level of RTBV coat protein was highly heritable (0.67) as estimated using the mean values of F3 lines, suggesting that selection for tolerance to RTBV can be performed in the early selfing generations using the technique employed in this study. The RTBV level had a negative correlation with plant height, but positive relationship with disease index value

Effect of thermal treatment on adsorption-desorption of ammonia and sulfur dioxide on palygorskite : change of surface acid-alkali properties

Thermally activated Palygorskite (Pg) has been found to be a good adsorbent material for ammonia (NH3) and sulfur dioxide (SO2). This research investigated the effect of thermal treatment on pore structure and surface acid-alkali properties of Pg through the adsorption-desorption of NH3 and SO2. The results showed that, up to 200 °C, the adsorption of NH3 on Pg was significantly higher than SO2. This was due to NH3 being adsorbed in the internal surface of Pg and forming hydrogen bonds (H-bonds) with coordinated water. The increase in thermal treatment temp. from 150 to 550 °C, showed a gradual decrease in the no. of surface acid sites, while the no. of surface alk. sites increased from 200 to 400 °C. The change of surface acidity-alk. sites is due to the collapse of internal channels of Pg and desorption of different types of hydroxyls assocd. with the Pg structure.

Morphine-induced receptor endocytosis in a novel knockin mouse reduces tolerance and dependence

Abstract Opioid drugs, such as morphine, are among the most effective analgesics available. However, their utility for the treatment of chronic pain is limited by side effects including tolerance and dependence. Morphine acts primarily through the mu-opioid receptor (MOP-R) , which is also a target of endogenous opioids. However, unlike endogenous ligands, morphine fails to promote substantial receptor endocytosis both in vitro, and in vivo. Receptor endocytosis serves at least two important functions in signal transduction. First, desensitization and endocytosis act as an "off" switch by uncoupling receptors from G protein. Second, endocytosis functions as an "on" switch, resensitizing receptors by recycling them to the plasma membrane. Thus, both the off and on function of the MOP-R are altered in response to morphine compared to endogenous ligands. To examine whether the low degree of endocytosis induced by morphine contributes to tolerance and dependence, we generated a knockin mouse that expresses a mutant MOP-R that undergoes morphine-induced endocytosis. Morphine remains an excellent antinociceptive agent in these mice. Importantly, these mice display substantially reduced antinociceptive tolerance and physical dependence. These data suggest that opioid drugs with a pharmacological profile similar to morphine but the ability to promote endocytosis could provide analgesia while having a reduced liability for promoting tolerance and dependence

Investing in the future : analysis of TxDOT 1547 Over-Axle Weight Tolerance Permits

The trucking industry has played a significant role in the economic growth in Texas by transporting and distributing commodities using commercial motor vehicles. The Texas Department of Transportation (TxDOT), however, has recognized that the large number of overweight trucks operating on the state highway system has resulted in the deterioration of pavement condition. In addition, the permit fee to carry higher loads above legal limits is much lower than the cost to treat the increase in pavement damage. The primary purpose of the research presented in this paper is to investigate current TxDOT overweight permit structures to support pavement management. The research team analyzed the TxDOT “1547” Over-axle Weight Tolerance Permit structure to support an increase in the fee structure, bringing it more in line with the actual pavement damage. The analysis showed that the revised overweight permit structure could provide an additional $9.3 million annually for pavement maintenance needs by increasing current permit fees. These results were supported by the 2030 Committee for recommendation to the Texas Transportation Commission and consideration by the State Legislature [1]. The research team recommends conducting further research to identify methods for working cooperatively with the trucking industry to develop improved methods for assessing weight damage relationships and developing more effective and accurate means for assessing overweight permit fees.

Tolerance, Freedom, Justice and Peace?: Britain, Australia and anti-Muslim Racism in the UK and Australia before 11 September 2001

Since 11 September 2001, Muslim minorities have experienced intensive "othering" in “Western” countries, above all in those US-led anglophone nations which invaded Afghanistan and Iraq to prosecute their "war on terror". This paper examines the cases of Britain and Australia, where whole communities of Muslims have been criminalised as "evil" and a "fifth column" enemy within by media, politicians, the security services and the criminal justice system. Although constituted by disparate ethnic groups, the targeted communities in each of these nations have experienced similar treatment in the State's anti-terrorist measures, as well as ideological responses and everyday racism, making comparable the two cases.