Effects of α-Terthienyl on the midgut detoxification enzymes of the European corn borer,Ostrinia nubilalis

The biochemical basis for the tolerance of the European corn borer,Ostrinia nubilalis, to the phototoxin-terthienyl was investigated by measuring the midgut polysubstrate monooxygenases and glutathioneS-transferase activities.-Terthienyl administered in the diet to the corn borers increased the level of cytochromeb ₅, NADH-cytochromec reductase,O-demethylase, and glutathioneS-transferase activities. The induced detoxification enzyme activities should enable the corn borer to metabolize-terthienyl more efficiently and therefore render the corn borer highly tolerant to-terthienyl.     

Persistence of nonprotein seed amino acid s-(β-carboxyethyl)-cysteine in young leaves ofCalliandra rubescens Ecological implications

The insecticidal nonprotein amino acid S-(-carboxyethyl)-cysteine (S-CEC) is the major free amino acid in the seeds of severalCalliandra spp. where it accounts for up to 2.9 % of dry weight. Lesser amounts of other related S-containing amino acids and an array of nonprotein imino acids derived from pipecolic acid are other constituents. High concentrations of imino acids, which also show insecticidal activity, are maintained in the mature leaves, but sulfur compounds are lacking. In this study the disappearance of S-CEC from the germinating seeds and young seedlings ofC. rubescens was monitored over time. After 10 weeks, S-CEC continues to be found in high concentrations in the stems and new leaves. As young leaves mature, sulfur compounds quickly decrease in concentration. Traces of S-CEC are found in new leaves of plants up to nine months after germination. Whether high concentration of S-CEC in young leaves is due to transportation from the seed or de novo synthesis is unclear. The ecological implications are discussed.     

Evaluation of the aromatic structure of coal tar pitch by solid and solution state n.m.r.

Rapid magic angle spinning has been used to obtain sideband-free high field ¹³C n.m.r. spectra of coal tar pitches in the solid state. However, the unfavourable cross-polarization and ¹H relaxation characteristics make it difficult to accurately estimate concentrations of quaternary aromatic carbon using the dipolar dephasing method. The concentrations of bridgehead aromatic carbon in the whole pitch and toluene-insoluble fraction investigated were deduced using a combination of solid and solution state n.m.r. and elemental analyses.     

Thiol Redox and pKa Properties of Mycothiol,the Predominant Low‐Molecular‐Weight Thiol Cofactor in the Actinomycetes

The thiol pK_a and standard redox potential of mycothiol, the major low‐molecular‐weight thiol cofactor in the actinomycetes, are reported. The measured standard redox potential reveals substantial discrepancies in one or more of the other previously measured intracellular parameters that are relevant to mycothiol redox biochemistry.     

Novel Redox-Dependent Esterase Activity (EC 3.1.1.2) for DJ-1: Implications for Parkinson’s Disease

Mutations the in human DJ-1 (hDJ-1) gene are associated with early-onset autosomal recessive forms of Parkinson’s disease (PD). hDJ-1/parkinsonism associated deglycase (PARK7) is a cytoprotective multi-functional protein that contains a conserved cysteine-protease domain. Given that cysteine-proteases can act on both amide and ester substrates, we surmised that hDJ-1 possessed cysteine-mediated esterase activity. To test this hypothesis, hDJ-1 was overexpressed, purified and tested for activity towards 4-nitrophenyl acetate (pNPA) as µmol of pNPA hydrolyzed/min/mg·protein (U/mg protein). hDJ-1 showed maximum reaction velocity esterase activity (V_max = 235.10 ± 12.00 U/mg protein), with a sigmoidal fit (S_0.5 = 0.55 ± 0.040 mM) and apparent positive cooperativity (Hill coefficient of 2.05 ± 0.28). A PD-associated mutant of DJ-1 (M26I) lacked activity. Unlike its protease activity which is inactivated by reactive oxygen species (ROS), esterase activity of hDJ-1 is enhanced upon exposure to low concentrations of hydrogen peroxide (<10 µM) and plateaus at elevated concentrations (>100 µM) suggesting that its activity is resistant to oxidative stress. Esterase activity of DJ-1 requires oxidation of catalytic cysteines, as chemically protecting cysteines blocked its activity whereas an oxido-mimetic mutant of DJ-1 (C106D) exhibited robust esterase activity. Molecular docking studies suggest that C106 and L126 within its catalytic site interact with esterase substrates. Overall, our data show that hDJ-1 contains intrinsic redox-sensitive esterase activity that is abolished in a PD-associated mutant form of the hDJ-1 protein.     

Evaluation of a delayed coking process by H and C n.m.r. spectroscopy: 2. Detailed interpretation of liquid n.m.r. spectra

The ¹H and ¹³C nuclear magnetic resonance (n.m.r.) spectra of a delayed coking feedstock and products, presented in a previous paper, are analysed here in detail by matching results from inspection of both nuclei. The conventional spectra of whole samples are used in combination with elemental analysis data, and substantial agreement is obtained. Differences are explored to yield valuable information. Interpretation of some band assignments is modified to account for new results. This approach results in a detailed quantitative estimation of a few key structures that contain the main functional groups that characterize these petroleum fractions.     

Activation of Ni/A12O3 catalysts through modification of the Al2O3 support

The effect of alumina pretreatment on the performance of alumina supported nickel catalysts was demonstrated in gas phase hydrogenation of toluene to methylcyclohexane. The state of the alumina was changed from pure to pure phase through various heat treatments in air. The catalysts were prepared from vapor phase by saturating the accessible binding sites on the pretreated alumina with the nickel precursor. The highest number of active sites for hydrogenation was observed for catalysts prepared on alumina having an incomplete phase transition and a / alumina phase ratio between 0.5 and 10. Results from temperature programmed desorption (TPD) studies revealed that a maximum in weakly chemisorbed hydrogen as well as in total amount of desorbed hydrogen was found for the same catalysts. By hydrogen chemisorption studies the total hydrogen uptake was found to correlate with the observed hydrogenation maximum. It is suggested that both the chemical and physical properties of the alumina influence the activity. An optimal metal-support interaction and structural defects on the alumina due to the phase transition can explain the observed maximum in the number of active sites and in hydrogen uptake.     

Oxidation behavior of 2.25Cr-1Mo steel with prior tempering at different temperatures

The oxidation behavior of a normalized 2.25Cr-1Mo steel tempered previously for 10 hr at different temperatures between 873 and 1023 K has been studied up to a maximum duration of 1000 hr in air at 773–973 K. The oxidation resistance of the steel was found to decrease significantly with the temperature of tempering. Tempering of this steel is reported to cause microstructural changes involving precipitation of Cr as carbides and a decrease in the effective (free) Cr contents, that could influence the oxidation resistance of the Cr-containing alloys. Relative compositions across the thickness of the oxide scales, as analyzed by SEM/EDX and SIMS, suggest that a less Cr-rich (and less protective) and thicker scale on the steel formed because previous tempering caused extensive depletion of free Cr.     

Nitrate and nitrite reduction of a sulphide-rich environment

A sulphide-rich anaerobic sludge acclimated with a molasses wastewater was used to carry out studies on nitrate and nitrite reductions in continuously stirred batch reactors. It was shown that a COD/N-NO_x ratio as high as 65·6 mg mg⁻¹ did not promote dissimilatory reduction of nitrogen oxides to ammonia. Denitrification was characterized by a probable accumulation of gaseous intermediates, nitric oxide (NO) and nitrous oxide (N₂O), by sulphide consumption with concomitant elemental sulphur production and by an increase of the redox potential. In addition, sulphate reducers were completely inhibited by nitrogenous oxides. Cultures performed without any carbon source proved that denitrifiers were able to use sulphides as electron donors. Furthermore, while a lag phase preceded nitrate denitrification, nitrite was consumed immediately. Chemical reduction of nitrite by ferrous iron (Fe²⁺) was considered to be responsible for this difference. Evidence of such a chemodenitrification has been presented by using a sterilized sludge which kept its ability to reduce nitrite while it lost its capacity to use nitrate. Moreover, this chemical activity was favoured by Fe²⁺ addition. Finally, it has been suggested that during the cultures performed with non-sterilized sludge, a biological reduction of the ferric ions (Fe³⁺) would be coupled to nitrite chemodenitrification and would allow a regeneration of Fe²⁺. © 1998 SCI