Effects of Metal Ions and Stabilisers on Peroxide Decomposition During Bleaching

A mathematical model has been formulated to allow the total peroxide consumption during bleaching of a mechanical pulp to be represented by two separate components; peroxide consumed in reactions with the pulp and peroxide decomposed in metal catalysed reactions. Using this models it is possible to determine the extent of metal catalysed peroxide decomposition in the presence of pulp. This method enables the effects of transition metal ions and stabilisers during bleaching to be studied directly. The use of constant pH conditions facilitates the direct comparison of the results obtained during bleaching with those obtained for analogous systems in the absence of pulp. The presence of pulp can exert a significant influence on the behaviour of transition metal ions and stabilisers towards peroxide decomposition. It appears that both the lignin and cellulose components can be responsible for the modifications in the catalytic behaviour observed in the presence of pulp. The effects of stabilisers on the rates of metal catalysed peroxide decomposition during bleaching cannot be predicted by studies conducted in the absence of pulp.     

Chemical Ecology and Sociality in Aphids: Opportunities and Directions

Aphids have long been recognized as good phytochemists. They are small sap-feeding plant herbivores with complex life cycles that can involve cyclical parthenogenesis and seasonal host plant alternation, and most are plant specialists. Aphids have distinctive traits for identifying and exploiting their host plants, including the expression of polyphenisms, a form of discrete phenotypic plasticity characteristic of insects, but taken to extreme in aphids. In a relatively small number of species, a social polyphenism occurs, involving sub-adult “soldiers” that are behaviorally or morphologically specialized to defend their nestmates from predators. Soldiers are sterile in many species, constituting a form of eusociality and reproductive division of labor that bears striking resemblances with other social insects. Despite a wealth of knowledge about the chemical ecology of non-social aphids and their phytophagous lifestyles, the molecular and chemoecological mechanisms involved in social polyphenisms in aphids are poorly understood. We provide a brief primer on aspects of aphid life cycles and chemical ecology for the non-specialists, and an overview of the social biology of aphids, with special attention to chemoecological perspectives. We discuss some of our own efforts to characterize how host plant chemistry may shape social traits in aphids. As good phytochemists, social aphids provide a bridge between the study of insect social evolution sociality, and the chemical ecology of plant-insect interactions. Aphids provide many promising opportunities for the study of sociality in insects, and to understand both the convergent and novel traits that characterize complex sociality on plants.     

Catalytic reactions of n-hexenes on amorphous silica-alumina

Reactions of n-hexenes on 80/100 mesh amorphous silica-alumina have been studied in a plug flow reactor at 405°C, and compared with results previously obtained using HY and H-ZSM-5. The dominant primary reaction is skeletal isomerization while the initial selectivity for cracking is very low compared to that on the zeolite catalysts. The dimerization-cracking reaction, the major cracking process on the zeolites, was not a primary reaction on amorphous silica-alumina. This and the slowness of reactions leading to paraffins and dehydrogenated species is attributed to the small number of strongly acidic sites on the amorphous material.     

High-resolution crystal structures of delta5-3-ketosteroid isomerase with and without a reaction intermediate analogue

Bacterial Delta5-3-ketosteroid isomerase (KSI) catalyzes a stereospecific isomerization of steroid substrates at an extremely fast rate, overcoming a large disparity of pKa values between a catalytic residue and its target. The crystal structures of KSI from Pseudomonas putida and of the enzyme in complex with equilenin, an analogue of the reaction intermediate, have been determined at 1.9 and 2.5 A resolution, respectively. The structures reveal that the side chains of Tyr14 and Asp99 (a newly identified catalytic residue) form hydrogen bonds directly with the oxyanion of the bound inhibitor in a completely apolar milieu of the active site. No water molecule is found at the active site, and the access of bulk solvent is blocked by a layer of apolar residues. Asp99 is surrounded by six apolar residues, and consequently, its pKa appears to be elevated as high as 9.5 to be consistent with early studies. No interaction was found between the bound inhibitor and the residue 101 (phenylalanine in Pseudomonas testosteroni and methionine in P. putida KSI) which was suggested to contribute significantly to the rate enhancement based on mutational analysis. This observation excludes the residue 101 as a potential catalytic residue and requires that the rate enhancement should be explained solely by Tyr14 and Asp99. Kinetic analyses of Y14F and D99L mutant enzymes demonstrate that Tyr14 contributes much more significantly to the rate enhancement than Asp99. Previous studies and the structural analysis strongly suggest that the low-barrier hydrogen bond of Tyr14 (>7.1 kcal/mol), along with a moderate strength hydrogen bond of Asp99 ( approximately 4 kcal/mol), accounts for the required energy of 11 kcal/mol for the transition-state stabilization.     

Low-frequency suppression of auditory nerve responses to characteristic frequency tones

The effects of low-frequency (50, 100, 200 and 400 Hz) 'suppressor' tones on responses to moderate-level characteristic frequency (CF) tones were measured in chinchilla auditory nerve fibers. Two-tone interactions were evident at suppressor intensities of 70-100 dB SPL. In this range, the average response rate decreased as a function of increasing suppressor level and the instantaneous response rate was modulated periodically. At suppression threshold, the phase of suppression typically coincided with basilar membrane displacement toward scala tympani, regardless of CF. At higher suppressor levels, two suppression maxima coexisted, synchronous with peak basilar membrane displacement toward scala tympani and scala vestibuli. Modulation and rate-suppression thresholds did not vary as a function of spontaneous activity and were only minimally correlated with fiber sensitivity. Except for fibers with CF < 1 kHz, modulation and rate-suppression thresholds were lower than rate and phase-locking thresholds for the suppressor tones presented alone. In the case of high-CF fibers with low spontaneous activity, excitation thresholds could exceed suppression thresholds by more than 30 dB. The strength of modulation decreased systematically with increasing suppressor frequency. For a given suppressor frequency, modulation was strongest in high-CF fibers and weakest in low-CF fibers. The present findings strongly support the notion that low-frequency suppression in auditory nerve fibers largely reflects an underlying basilar membrane phenomenon closely related to compressive non-linearity.     

Sj?gren''s syndrome in patients with newly diagnosed untreated non-Hodgkin''s lymphoma

A prfA gene encoding polypeptide release factor RF1 was cloned from Thermus thermophilus. T thermophilus RF1 shares 68% homology with Escherichia coli RF1, and its overproduction reduced readthrough translation of UAG, not of UGA, in the lacZ gene. Rapid purification of T thermophilus RF1 was achieved by T7-RNA polymerase driven overexpression of T thermophilus RF1 protein with a C-terminal histidine tag.     

Superconducting gap function and upper critical field in the presence of inhomogeneous magnetic order

Rare earth ternary superconductors are known to exhibit oscillatory magnetic orders below their superconducting transition temperatures. The study of behaviour of superconducting electrons in an inhomogeneous magnetic field is therefore important for such systems. We report here the results of our theoretical study of superconducting gap function Δ(T) and upper critical fieldH _c2 (T). The results are applied to analyse and explain the variation of Δ(T) andH _c2 (T) in case of NdRh₄B₄.