Spool valve mechanism used in a 20 K Gifford-McMahon cycle cryorefrigerator and its effect on the P-V diagram

The design and fabrication of a spool valve for a two-stage Gifford-McMahon cycle cryorefrigerator is described. The effect of this valve on the P-V diagram and practical methods of reducing the P-V degradation are also discussed.

Catalysis and mechanism of malonyl transferase activity in type II fatty acid biosynthesis acyl carrier proteins

One of the unexplored, yet important aspects of the biology of acyl carrier proteins (ACPs) is the self-acylation and malonyl transferase activities dedicated to ACPs in polyketide synthesis. Our studies demonstrate the existence of malonyl transferase activity in ACPs involved in type II fatty acid biosynthesis from Plasmodium falciparum and Escherichia coli. We also show that the catalytic malonyl transferase activity is intrinsic to an individual ACP. Mutational analysis implicates an arginine/lysine in loop II and an arginine/glutamine in helix III as the catalytic residues for transferase function. The hydrogen bonding properties of these residues appears to be indispensable for the transferase reaction. Complementation of fabD(Ts) E. coli highlights the putative physiological role of this process. Our studies thus shed light on a key aspect of ACP biology and provide insights into the mechanism involved therein.

Mechanism of high-temperature superconductivity in YBa2Cu3O7−δ: Crucial role of oxygen

Oxygen atoms in the middle Cu---O layer of YBa2Cu3O7 consisting of strings of corner-connected (CuO4)∞ units are shown to be crucial for superconductivity. Importance of hole-hole pairing giving rise to O---O bonds is also indicated.

Metal Chelates in Vinyl Polymerization: Kinetics and Mechanism of Acrylonitrile Polymerization Initiated by Cu(I1) Imine Complexes

The free radical polymerization of acrylonitrile (AN) initiated by Cu(I1) 4-anilino 3-pentene 2-one [Cu(II) ANIPO] Cu(II), 4-p-toluedeno 3-pentene 2-one [Cu(II) TPO], and Cu(I1) 4-p-nitroanilino 3-pentene 2-one [Cu(II) NAPO] was studied in benzene at 50 and 60°C and in carbon tetrachloride (CCld), dimethyl sulfoxide (DMSO), and methanol (MeOH) at 60°C. Although the polymerization proceeded in a heterogeneous phase, it followed the kinetics of a homogeneous process. The monomer exponents were 22 at two different temperatures and in different solvents. The square-root dependence of R, on initiator concentration and higher monomer exponents accounted for a 1:2 complex formation between the chelate and monomer. The complex formatign was shown by ultraviolet (UV) study. The activation energies, kinetics, and chain transfer constants were also evaluated.

Mechanism of oxidation of α,β-unsaturated thiones by singlet oxygen

Photo-oxidation of α,β-unsaturated thiones yields the corresponding ketones as the only product. Studies carried out on three systems, namely thioketones, α,β-unsaturated thiones and thioketenes, have revealed that there exists a similarity in their mechanism of oxidation. It has been suggested that the thiocarbonyl chromophore is the site of attack by singlet oxygen in α,β-unsaturated thiones and that the adjacent C-C double bond is inert under these conditions. Absence of sulphine during the oxidation of α,β-unsaturated thiones is attributed to the electronic factors operating on the zwitterionic/diradical intermediate. While α,β-unsaturated ketones are poorly reactive, α,β-unsaturated thiones are highly reactive toward singlet oxygen.

Mechanism of catalytic activity of metal oxides and chromites on ammonium perchlorate pyrolysis

This study investigates the mechanism of action of transition metal chromites on the decomposition of ammonium perchlorate.

Ruminococcus bromii, identification and isolation as a dominant community member in the rumen of cattle fed a barley diet

Aims: To identify dominant bacteria in grain (barley)-fed cattle for isolation and future use to increase the efficiency of starch utilization in these cattle. Methods and Results: Total DNA was extracted from samples of the rumen contents from eight steers fed a barley diet for 9 and 14 days. Bacterial profiles were obtained using denaturing gradient gel electrophoresis (DGGE) of the PCR-amplified V2/V3 region of the 16S rRNA genes from total bacterial DNA. Apparently dominant bands were excised and cloned, and the clone insert sequence was determined. One of the most common and dominant bacteria present was identified as Ruminococcus bromii. This species was subsequently isolated using traditional culture-based techniques and its dominance in the grain-fed cattle was confirmed using a real-time Taq nuclease assay (TNA) designed for this purpose. In some animals, the population of R. bromii reached densities above 1010R. bromii cell equivalents per ml or approximately 10% of the total bacterial population. Conclusions: Ruminococcus bromii is a dominant bacterial population in the rumen of cattle fed a barley-based diet. Significance and Impact of the Study: Ruminococcus bromii YE282 may be useful as a probiotic inoculant to increase the efficiency of starch utilization in barley-fed cattle. The combination of DGGE and real-time TNA has been an effective process for identifying and targeting for isolation, dominant bacteria in a complex ecosystem.

Dry sliding wear behaviour of magnesium alloy based hybrid composites in the longitudinal direction

In the present investigation, the wear behaviour of a creep-resistant AE42 magnesium alloy and its composites reinforced with Saffil short fibres and SiC particles in various combinations is examined in the longitudinal direction i.e., the plane containing random fibre orientation is perpendicular to the steel counter-face. Wear tests are conducted on a pin-on-disc set-up under dry sliding condition having a constant sliding velocity of 0.837 m/s for a constant sliding distance of 2.5 km in the load range of 10-40 N. It is observed that the wear rate increases with increase in load for the alloy and the composites, as expected. Wear rate of the composites is lower than the alloy and the hybrid composites exhibit a lower wear rate than the Saffil short fibres reinforced composite at all the loads. Therefore, the partial replacement of Saffil short fibres by an equal volume fraction of SiC particles not only reduces the cost but also improves the wear resistance of the composite. Microstructural investigation of the surface and subsurface of the worn pin and wear debris is carried out to explain the observed results and to understand the wear mechanisms. It is concluded that the presence of SiC particles in the hybrid composites improves the wear resistance because these particles remain intact and retain their load bearing capacity even at the highest load employed, they promote the formation of iron-rich transfer layer and they also delay the fracture of Saffil short fibres to higher loads. Under the experimental conditions used in the present investigation, the dominant wear mechanism is found to be abrasion for the AE42 alloy and its composites. It is accompanied by severe plastic deformation of surface layers in case of alloy and by the fracture of Saffil short fibres as well as the formation of iron-rich transfer layer in case of composites.

Structures of mannose-6-phosphate isomerase from Salmonella typhimurium bound to metal atoms and substrate: implications for catalytic mechanism

Mannose-6-phosphate isomerase (MPI) catalyzes the inter-conversion of mannose 6-phosphate and fructose 6-phosphate. X-ray crystal structures of MPI from Salmonella typhimurium in the apo form (with no metal bound) and in the holo form (with bound Zn2+) and two other structures with yttrium bound at an inhibitory site and complexed with Zn2+ and fructose 6-phosphate (F6P) were determined in order to gain insights into the structure and the isomerization mechanism. Isomerization involves acid/base catalysis with proton transfer between the C1 and C2 atoms of the substrate. His99, Lys132, His131 and Asp270 are close to the substrate and are likely to be the residues involved in proton transfer. The interactions observed at the active site suggest that the ring-opening step is probably catalyzed by His99 and Asp270. An active-site loop consisting of residues 130-133 undergoes conformational changes upon substrate binding. Zn2+ binding induces structural order in the loop consisting of residues 50-54. The metal atom appears to play a role in substrate binding and is probably also important for maintaining the architecture of the active site. Isomerization probably follows the previously suggested cis-enediol mechanism.

A mechanism for the west-north-west movement of monsoon depressions

The monsoon depressions intensify over the Bay of Bengal, move in a west-north-west (WNW) direction and dissipate over the Indian continent. No convincing physical explanation for their observed movement has so far been arrived at, but here, I suggest why the maximum precipitation occurs in the western sector of the depression and propose a feedback mechanism for the WNW movement of the depressions. We assume that a heat source is created over the Bay of Bengal due to organization of cumulus convection by the initial instability. In a linear sense, heating at this latitude (20° N), produces an atmospheric response mainly in the form of a stationary Rossby–gravity wave to the west of the heat source. The low-level vorticity (hence the frictional convergence) and the vertical velocity associated with the steady-state response is such that the maximum moisture convergence (and precipitation) is expected to occur in the WNW sector at a later time. Thus, the heat source moves to the WNW sector at a later time and the feedback continues resulting in the WNW movement of the depressions.

Kinetics and mechanism of anodic oxidation of chlorate ion to perchlorate ion on lead dioxide electrodes

The kinetics and mechanism of anodic oxidation of chlorate ion to perchlorate ion on titanium-substrate lead dioxide electrodes have been investigated experimentally and theoretically. It has been demonstrated that the ionic strength of the solution has a marked effect on the rate of perchlorate formation, whereas the pH of the solution does not influence the reaction rate. Experimental data have also been obtained on the dependence of the reaction rate on the concentration of chlorate ion in the solution at constant ionic strength. With these data, diagnostic kinetic criteria have been deduced and compared with corresponding quantities predicted for various possible mechanisms including double layer effects on electrode kinetics. It has thus been shown that the most probable mechanisms for anodic chlorate oxidation on lead dioxide anodes involve the discharge of a water molecule in a one-electron transfer step to give an adsorbed hydroxyl radical as the rate-determining step for the overall reaction.

Kinetics Of The Aminolysis Reactions Of Chlorocyclotriphosphazenes-Changeover From A Sn2(P) To A Sn1(P) Mechanism

A change-over from SN2(P) to SN1(P) mechanism is established for the chlorine replacement reactions of halogenocyclophosphazenes; this mechanistic change-over helps in rationalising the diverse findings reported for this class of reactions.

Tree growth relationships and silvicultural tools to assist stand management in private native spotted gum dominant forests in Queensland and northern New South Wales.

Spotted gum dominant forests occur from Cooktown in northern Queensland (Qld) to Orbost in Victoria (Boland et al. 2006) and these forests are commercially very important with spotted gum the most commonly harvested hardwood timber in Qld and one of the most important in New South Wales (NSW). Spotted gum has a wide range of end uses from solid wood products through to power transmission poles and generally has excellent sawing and timber qualities (Hopewell 2004). The private native forest resource in southern Qld and northern NSW is a critical component of the hardwood timber industry (Anon 2005, Timber Qld 2006) and currently half or more of the native forest timber resource harvested in northern NSW and Qld is sourced from private land. However, in many cases productivity on private lands is well below what could be achieved with appropriate silvicultural management. This project provides silvicultural management tools to assist extension staff, land owners and managers in the south east Qld and north eastern NSW regions. The intent was that this would lead to improvement of the productivity of the private estate through implementation of appropriate management. The other intention of this project was to implement a number of silvicultural experiments and demonstration sites to provide data on growth rates of managed and unmanaged forests so that landholders can make informed decisions on the future management of their forests. To assist forest managers and improve the ability to predict forest productivity in the private resource, the project has developed: • A set of spotted gum specific silvicultural guidelines for timber production on private land that cover both silvicultural treatment and harvesting. The guidelines were developed for extension officers and property owners. • A simple decision support tool, referred to as the spotted gum productivity assessment tool (SPAT), that allows an estimation of: 1. Tree growth productivity on specific sites. Estimation is based on the analysis of site and growth data collected from a large number of yield and experimental plots on Crown land across a wide range of spotted gum forest types. Growth algorithms were developed using tree growth and site data and the algorithms were used to formulate basic economic predictors. 2. Pasture development under a range of tree stockings and the expected livestock carrying capacity at nominated tree stockings for a particular area. 3. Above-ground tree biomass and carbon stored in trees. •A series of experiments in spotted gum forests on private lands across the study area to quantify growth and to provide measures of the effect of silvicultural thinning and different agro-forestry regimes. The adoption and use of these tools by farm forestry extension officers and private land holders in both field operations and in training exercises will, over time, improve the commercial management of spotted gum forests for both timber and grazing. Future measurement of the experimental sites at ages five, 10 and 15 years will provide longer term data on the effects of various stocking rates and thinning regimes and facilitate modification and improvement of these silvicultural prescriptions.

Impression creep of zinc and the rate-controlling dislocation mechanism of plastic flow at high temperatures

The impression creep behaviour of zinc is studied in the range 300 to 500 K and the results are compared with the data from conventional creep tests. The steady-state impression velocity is found to exhibit the same stress and temperature dependence as in conventional tensile creep with the same power law stress exponent. Also studied is the effect of indenter size on the impression velocity. The thermal activation parameters for plastic flow at high temperatures derived from a number of testing techniques agree reasonably well. Grain boundary sliding is shown to be unimportant in controlling the rate of plastic flow at high temperatures. It is observed that the Cottrell-Stokes law is obeyed during high-temperature deformation of zinc. It is concluded that a mechanism such as forest intersection involving attractive trees controls the high-temperature flow rather than a diffusion mechanism.