Structure and mechanism of action of isopentenylpyrophosphate-dimethylallylpyrophosphate isomerase

We have obtained the three-dimensional X-ray crystallographic structure of a C67A mutant Escherichia coli isopentenylpyrophosphate-dimethylallylpyrophosphate isomerase (EC 5.3.3.2) complexed with the bromohydrin of isopentenylpyrophosphate, at 1.93 A resolution. The overall backbone fold is very similar to that obtained previously for the wild-type enzyme in the presence of a divalent metal cation (Mn2+ or Mg2+). However, in the new structure, there are two metal binding sites, not just one. The first metal binding site is occupied by Mn2+, coordinated to three histidine and two glutamate residues, while the second is occupied by Mg2+, coordinated to two bromohydrin-ligand phosphate oxygens, the carbonyl oxygen of A67, a carboxyl oxygen of E87, and two water molecules. The C3 hydroxyl group of the bromohydrin inhibitor is involved in a short hydrogen bond to the carboxyl group of E116, one of the two Mn-bound glutamates. The structure obtained is consistent with a mechanism of action of the enzyme in which the carboxyl group of E116 protonates the double bond in isopentenylpyrophosphate, forming a carbocation, followed by removal of a C2 proton by the thiolate of C67, in the wild-type enzyme. The inhibition of the enzyme by a wide variety of other potent inhibitors is also readily explained on the basis of the bromohydrin inhibitor structure.     

Evidence for the involvement of silver nanoclusters during the Wolff rearrangement of alpha-diazoketones

In situ-generated silver nanoclusters(Ag(n)) during the reduction of either silver(I) oxide or other salts presumably catalyze the Wolff rearrangement of alpha-diazoketones. Their optical, physical, and catalytic properties depend on the starting silver(I) compound and the reaction conditions. [reaction: see text]     

Dependence Properties of Multivariate Mixture Distributions and Their Applications

Consider a multivariate mixture model where the random variables X ₁, ..., X _n given (₁, ..., _n ), are conditionally independent. Conditions are obtained under which different kinds of positive dependence hold among X _i 's. The results obtained are applied to a variety of problems including the concomitants of order statistics and of record values; and to frailty models.     

Work allocation to stations with varying learning slopes and without buffers

In this paper, we address the problem of allocating the work elements, belonging to the products of a lot, to the stations of an assembly line so as to minimize the makespan. The lots that are processed on the assembly line are characterized by a low overall demand for each product. There is no buffer permitted in between the stations, and the line operates under learning. In particular, the stations’ learning slopes are assumed to be different. We present a procedure to determine the optimal assignments of the workload to the stations under learning variability and show that it considerably affects these assignments.     

First enantiospecific synthesis of (+)-β-herbertenol

The first enantiospecific synthesis of (+)-β-herbertenol, from naturally occurring R-(+)-citronellal, employing Taber's diazo decomposition protocol as the key step, is described.     

Analysis of current-voltage characteristics of inhomogeneous Schottky diodes at low temperatures

Two approaches of Gaussian distribution of barrier heights in inhomogeneous Schottky diodes have been analyzed by comparing the results for consistency between the two. For this the current-voltage characteristics of inhomogeneous Schottky diodes have been generated by using analytically solved thermionic-emission diffusion equation incorporating Gaussian distribution of barrier heights and by direct numerical integration over a barrier height range. The differences in the results obtained in two approaches are discussed and it is shown that the two approaches yield current-voltage characteristics with slightly different features. The discrepancies in the results obtained in two approaches are attributed to the same series resistance assumed for all elementary barriers of the distribution. It is shown that assigning same series resistance to all barrier of the distribution in numerical integration approach causes current saturation at low bias and inhibits intersection of current-voltage curves from being observable which otherwise occurs in the curves obtained using analytical equation. The paper deals with these aspects in details.     

Reputation and efficiency: A non-parametric assessment of America’s top-rated MBA programs

Widely publicized reports of fresh MBAs getting multiple job offers with six-figure annual salaries leave a long-lasting general impression about the high quality of selected business schools. While such spectacular achievement in job placement rightly deserves recognition, one should not lose sight of the resources expended in order to accomplish this result. In this study, we employ a measure of Pareto-Koopmans global efficiency to evaluate the efficiency levels of the MBA programs in Business Week’s top-rated list. We compute input- and output-oriented radial and non-radial efficiency measures for comparison. Among three tier groups, the schools from a higher tier group on average are more efficient than those from lower tiers, although variations in efficiency levels do occur within the same tier, which exist over different measures of efficiency.     

Densities, speeds of sound and viscosities of binary liquid mixtures of octan-2-ol with benzene and halobenzenes at 298.15 and 303.15 K

Densities ρ, speeds of sound u, viscosities η and refractive indices n_D of binary mixtures of octan-2-ol with benzene, chlorobenzene and bromobenzene have been measured over the entire range of composition at 298.15 and 303.15 K and atmospheric pressure. From the experimental data, excess molar volumes V^E, isentropic compressibilities κ_S, excess isentropic compressibilities κ_S^E, and deviations of speeds of sound u^D, have been calculated at 298.15 and 303.15 K. These excess functions have been fitted to the Redlich-Kister polynomial equation. The viscosity data have been correlated using Kendall-Monroe, Grunberg-Nissan, Tamura-Kurata, Hind-Mclaughlin Ubbelohde and Katti-Chaudhary viscosity models, and McAllister's three-body interaction model at different temperatures.