Reactivity in the spinel formation reaction in CuO/Al2O3, Fe2O3, Cr2O3 systems

Abstract is not available.

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.

Topochemical dimerization of non-parallel double bonds: 7-methoxycoumarin

X-ray crystal structure analysis of 7-methoxycoumarin reveals that the reactive double bonds are rotated by about 65° with respect to each other, the centre-to-centre distance between the double bonds being 3.83 Å. In spite of this unfavourable arrangement, photodimerization occurs in the crystalline state yielding the syn-head-tail dimer as the only product. Lattice energy calculations on ground-state molecules in crystals throw light on the mechanism of the reaction.

Some mechanisms of excitation of a railway wheel

Railway wheel vibrations are caused by a number of mechanisms. Two of these are considered: (a) gravitational load reaction acting on different points of the wheel rim, as the wheel rolls on, and (b) random fluctuating forces generated at the contact patch by roughness on the mating surfaces of the wheel and rail. The wheel is idealized as a thin ring, and the analysis is limited to a single wheel rolling on a rail. It is shown that the first mechanism results in a stationary pattern of vibration, which would not radiate any sound. The acceleration caused by roughness-excited forces is much higher at higher frequencies, but is of the same order as that caused by load reaction at lower frequencies. The computed acceleration level (and hence the radiated SPL) caused by roughness is comparable with the observed values, and is seen to increase by about 10 dB for a doubling of the wagon speed. The driving point impedance of the periodic rail-sleeper system at the contact patch, which is used in the analysis, is derived in a companion paper.

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.

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.

Metal chelates in vinyl polymerization: Kinetics and mechanism of acrylonitrile polymerization initiated by Cu(II) imine complexes

The free radical polymerization of acrylonitrile (AN) initiated by Cu(II) 4-anilino 2-one [Cu(II) ANIPO] Cu(II), 4-p-toluedeno 3-pentene 2-one [Cu(II) TPO], and Cu(II) 4-p-nitroanilino 3-pentene 2-one [Cu(II) NAPO] was studied in benzene at 50 and 60°C and in carbon tetrachloride (CCl4), 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 2 at two different temperatures and in different solvents. The square-root dependence of Rp on initiator concentration and higher monomer exponents accounted for a 1:2 complex formation between the chelate and monomer. The complex formation was shown by ultraviolet (UV) study. The activation energies, kinetics, and chain transfer constants were also evaluated.

Nondeactivating Nanosized Ionic Catalysts for Water-Gas Shift Reaction

The water-gas shift reaction (WGS) is an important reaction to produce hydrogen. In this study, we have synthesized nanosized catalysts where Pt ion is substituted in the +2 state in TiO2, CeO2, and Ce1-xTixO2-delta. These catalysts have been characterized by X-ray diffraction and X-ray photoelectron spectroscopy (XPS), and it has been shown that Pt2+ in these reducible oxides result in solid solutions like Ti0.99Pt0.01O2-delta, Ce0.8Ti0.15Pt0.02O2-delta, and Ce0.98Pt0.02O2-delta. These catalysts were tested for the water gas shift reaction both ill the presence and absence of hydrogen. It was shown that Ti0.99Pt0.01O2-delta exhibited higher catalytic activity than Ce0.83Ti0.15Pt0.02O2-delta and Ce0.98Pt0.02O2-delta. Further, experiments were conducted to determine the deactivation of these catalysts. There was no sintering of Pt and no carbonate formation; therefore, the catalyst did not deactivate even after prolonged reaction. There was no carbonate formation because of the highly acidic nature of Ti4+ ions in the catalysts.

Reactivity of rice husk ash

Effect of lime:silica ratio on the kinetics of the reaction of silica with saturated lime has been investigated. Below C/S=0.65 the reaction does not proceed to completion and even in the presence of a large excess of silica only 90% lime is consumed. A parameter, lime reactivity index, has been defined to quantity the reactive silica present in rice husk ash. The product of the reaction between rice husk ash and saturated lime is a calcium hydrosilicate, C---S---H(I)**. The fibrilar structure and the hollow tubular morphology of the fibres of C---S---H, have been explained by a growth mechanism, where the driving force is osmotic pressure.

Surface segregation and oxidation studies of Cu-Sn and Cu-Pd alloys by x-ray photoelectron and auger spectroscopy

X-ray photoelectron and Auger spectroscopic techniques have been employed to study surface segregation and oxidation of Cu-1 at%Sn, Cu-9at%Pd and Cu-25at%Pd alloys. Both Cu-Pd(9%) and Cu-Pd(25%) alloys show segregation of Cu when heated above 500 K. The Pd concentration was reduced by 50% at 750 K compared to the bulk composition; the enthalpy of segregation of Cu is around - 6kJ/mol. Sn segregation is seen from 470 to 650 K in the Cu-Sn(1%) alloy, and a saturation plateau of Sn concentration above 650 K is observed. Surface oxidation of Cu-Sn(1%) and Cu-Pd(9%) alloys at 500 K showed the formation of Cu2O on the surface with total suppression of Sn or Pd on the respective alloy surfaces. On vacuum annealing the oxidised Cu-Sn alloy surface at 550 K, a displacement reaction 2Cu2O+Sn→4Cu+SnO2 was observed. However, under similar annealing of the oxidised Cu-Pd(9%) alloy surface at 500 K, oxide oxygen was totally desorbed leaving the Cu-Pd alloy surface clean. In the case of the Cu-Pd(25%) alloy, only dissociatively chemisorbed oxygen was seen at 500 K which desorbed at the same temperature. Oxygen spill-over from copper to palladium is suggested as the mechanism of oxygen desorption from the oxidised Cu-Pd alloy surfaces.

Kinetic mechanism of the interaction of D-cycloserine with serine hydroxymethyltransferase

The kinetic mechanism for the interaction of D-cycloserine with serine hydroxymethyltransferase (EC2.1.2.1) from sheep liver was established by measuring changes in the activity, absorbance, and circular dichoism (CD) of the enzyme. The irreversible inhibition of the enzyme was characterized by three detectable steps: an initial rapid step followed by two successive steps with rate constants of 5.4 X s-l and 1.4 X lo4 s-l. The first step was distinguished by a rapid disappearance of the enzyme absorbance peak at 425 nm, a decrease in the enzyme activity to 25% of the uninhibited velocity, and a lowering of the CD intensity at 432 nm to about 65% of the original value. The second step of the interaction was accompanied by a complete loss of enzyme.

Reaction of Hexachlorocyclotriphosphazene with Sodium p-Cresoxide

The reaction of hexachlorocyclotriphosphazene (N3P3Cl6) with sodium p-cresoxide proceeds by a predominantly nongeminal pathway. The presence of geminal isomers at the bis- and tris-stages of substitution in tiny quantities (< 5%) has also been observed. All the chloro(p-cresoxy)cyclotriphosphazenes and their dimethylamino derivatives have been characterized by 1H-, 13C{1H}-, and 31P{1H}-NMR spectroscopy. The reaction of N3P3Cl6 with sodium phenoxide has been reinvestigated. The relative yields of the products at various stages of substitution and their isomeric compositions are almost the same for both phenoxy and p-cresoxy systems. Possible mechanisms to explain the observed isomeric compositions are discussed. A through-space interaction involving oxygen-2p and phosphorus-3d orbitals is invoked to explain the greater yield of the cis isomer of N3P3Cl4(OAr)2 than that of its trans isomer.