Analysis and computation of the oil film thickness between the piston ring and cylinder liner of an internal combustion engine

A study of the essential features of piston rings in the cylinder liner of an internal combustion engine reveals that the lubrication problem posed by it is basically that of a slider bearing. According to steady-flow-hydrodynamics, viz. Image the oil film thickness becomes zero at the dead centre positions as the velocity, U = 0. In practice, however, such a phenomenon cannot be supported by consideration of the wear rates of pistion rings and cylinder liners. This can be explained by including the “squeeze” action term in the

Role of orbital symmetry in transition metal promoted ring opening reactions of methylenecyclopropanes and cyclobutenes

Transition metals catalyse a variety of organic reactions, of which the ring opening of strained ring organic molecules generated a lot of interest. Theoreticians predicted a metal orbital catalysed pathway, which involved concerted bond breaking and bond forming. On the other hand experimentalists were able to show that the reaction was not proceeding through a concerted pathway by intercepting the intermediates involved. There remained, however, two ring systems methylenecyclopropanes and cyclobutenes—whose reactions with metal complexes seemed to be of a concerted nature. An analysis of the reactions of different metal complexes with these ring systems and the theoretical predictions provide a rationale for understanding these reactions.

Mechanism of adsorption effects on electrode kinetics: Part I: Selection rules in the case of low coverage by molecular surfactants

It is shown that the effect of adsorption of inert molecules on electrode reaction rates is completely accounted for, by introducing into the rate equation, adsorption-induced changes in both the effective electrode area as well as in the electrostatic potential at the reaction site with an additional term for the noncoulombic interaction between the reactant and the adsorbate. The electrostatic potential at the reaction site due to the adsorbed layer is calculated using a model of discretely-distributed molecules in parallel orientation when adsorbed on the electrode with an allowance for thermal agitation. The resulting expression, which is valid for the limiting case of low coverages, is used to predict the types of molecular surfactants that are most likely to be useful for acceleration and inhibition of electrode reactions.

Jumping numbers of a simple complete ideal in a two-dimensional regular local ring

The multiplier ideals of an ideal in a regular local ring form a family of ideals parametrized by non-negative rational numbers. As the rational number increases the corresponding multiplier ideal remains unchanged until at some point it gets strictly smaller. A rational number where this kind of diminishing occurs is called a jumping number of the ideal. In this manuscript we shall give an explicit formula for the jumping numbers of a simple complete ideal in a two dimensional regular local ring. In particular, we obtain a formula for the jumping numbers of an analytically irreducible plane curve. We then show that the jumping numbers determine the equisingularity class of the curve.

A new mode of ring cleavage of 2,3-dihydroxybenzoic acid in Tecoma stans (L.). Partial purification and properties of 2,3-dihydroxybenzoate 2,3-oxygenase.

2,3-Dihydroxybenzoic acid has been shown to be oxidized via the 3-oxoadipate pathway in the leaves of Tecoma stans. The formation of 2-carboxy-cis,cis-muconic acid, a muconolactone, 3-oxoadipic acid and carbon dioxide during its metabolism has been demonstrated using an extract of Tecoma leaves. The first reaction of the pathway, viz., the conversion of 2,3-dihydroxybenzoate to 2-carboxy-cis,cis-muconic acid has been shown to be catalysed by an enzyme designated as 2,3-dihydroxybenzoate 2,3-oxygenase. The enzyme has been partially purified and a few of its properties studied. The enzyme is very labile with a half-life of 3--4 h. It is maximally active with 2,3-dihydroxybenzoate as the substrate and does not exhibit any activity with catechol, 4-methyl catechol, 3,4-dihydroxybenzoic acid, etc. However, 2,3-dihydroxy-p-toluate and 2,3-dihydroxy-p-cumate are also oxidized by the enzyme by about 38% and 28% respectively, compared to 2,3-dihydroxybenzoate. Sulfhydryl reagents inhibit the enzyme reaction and the inhibition can be prevented by preincubation of the enzyme with the substrate. Substrate also affords protection to the enzyme against thermal inactivation. Sulfhydryl compounds strongly inhibit the reaction and the inhibition cannot be prevented by preincubation of the enzyme with its substrates. Data on the effect of metal ions as well as metal chelating agents suggest that copper is the metal cofactor of the enzyme. Evidence is presented which suggests that iron may not be participating in the overall catalytic mechanism.

A Comparative Study of Electrochemical Kinetic Parameters by the Potential Step Method. Electrode Reactions of CyDTA and EDTA Complexes of Cu(II) at DME

By using the same current-time (I-t) curves, electrochemical kinetic parameters are determined by two methods, (a) using the ratio of current at a given potential to the diffusion-controlled limiting current and (b) curve fitting method, for the reduction of Cu(II)–CyDTA complex. The analysis by the method (a) shows that the rate determining step involves only one electron although the overall reduction of the complex involves two electrons suggesting thereby the stepwise reduction of the complex. The nature of I-t curves suggests the adsorption of intermediate species at the electrode surface. Under these circumstances more reliable kinetic parameters can be obtained by the method (a) compared to that of (b). Similar observations are found in the case of reduction of Cu(II)–EDTA complex.

Pyrrolidine ring conformations in prolyl peptides from 13C spin-lattice relaxation times

A method was developed in the framework of a bistable jump model to obtain the pyrrolidine ring conformations in proline peptides from 13C spin-lattice relaxation times. Equations are presented expressing the ring torsions in terms of the 13C spin-lattice relaxation times of the ring carbons. This method was applied to 26 pyrrolidine ring systems and acceptable conformations were obtained.