Reactions of (PCP)Ru(CO)(NHPh)(PMe3) (PCP = 2,6-(CH2PtBu2)2C6H3) with substrates that possess polar bonds

The Ru(II) amido complex (PCP)Ru(CO)(PMe(3))(NHPh) (1) (PCP = 2,6-(CH(2)P(t)Bu(2))(2)C(6)H(3)) reacts with compounds that possess polar C=N, C triple bond N, or C=O bonds (e.g., nitriles, carbodiimides, or isocyanates) to produce four-membered heterometallacycles that result from nucleophilic addition of the amido nitrogen to an unsaturated carbon of the organic substrate. Based on studies of the reaction of complex 1 with acetonitrile, the transformations are suggested to proceed by dissociation of trimethylphosphine, followed by coordination of the organic substrate and then intramolecular N-C bond formation. In the presence of ROH (R = H or Me), the fluorinated amidinate complex (PCP)Ru(CO)(N(Ph)C(C(6)F(5))NH) (6) reacts with excess pentafluorobenzonitrile to produce (PCP)Ru(CO)(F)(N(H)C(C(6)F(5))NHPh) (7). The reaction with MeOH also produces o-MeOC(6)F(4)CN (>90%) and p-MeOC(6)F(4)CN (<10%). Details of the solid-state structures of (PCP)Ru(CO)(F)(N(H)C(C(6)F(5))NHPh) (7), (PCP)Ru(CO)[PhNC{NH(hx)}N(hx)] (8), (PCP)Ru(CO){N(Ph)C(NHPh)O} (9), and (PCP)Ru(CO){OC(Ph)N(Ph)} (10) are reported.     

Enantioseparation of citalopram analogues with sulfated β‐cyclodextrin by capillary electrophoresis

Capillary electrophoresis methods were developed for the enantiomeric separation of 27 citalopram analogues. Sulfated β‐cyclodextrin was the most broadly selective and useful chiral selector. The separations of most of the citalopram analogue compounds reported in this work have not been reported previously. Excellent enantiomeric separations were obtained for 26 out of 27 compounds, and most of the separations were achieved within 10 min. The effects of chemical parameters such as chiral selector types, buffer types, chiral selector and buffer concentrations, buffer pH and organic modifiers on the separation were investigated. The influence of analyte structure on separation also was examined and discussed.     

Intermolecular cross-double-michael addition between nitro and carbonyl activated olefins as a new approach in C-C bond formation

A novel intermolecular cross-double-Michael addition between nitro and carbonyl activated olefins has been developed through Lewis base catalysis. The reaction took place with a large group of beta-alkyl nitroalkenes and alpha,beta-unsaturated ketone/esters, producing an allylic nitro compound in good to excellent yields.     

Measurement of the rate coefficient of the reaction CH+O2 → products in the temperature range 2200 to 2600 K

The rate coefficient of the reaction CH+O₂ → products was determined by measuring CH-radical concentration profiles in shock-heated 100–150 ppm ethane/1000 ppm O₂ mixtures in Ar using cw, narrow-linewidth laser absorption at 431.131 nm. Comparing the measured CH concentration profiles to ones calculated using a detailed kinetics model, yielded the following average value for the rate coefficient independent of temperature over the range 2200–2600 K: The experimental conditions were chosen such that the calculated profiles were sensitive mainly to the reactions CH+O₂ → products and CH₃+M → CH+H₂+M. For the methyl decomposition reaction channel, the following rate-coefficient expression provided the best fit of the measured CH profiles: Additionally, the rate coefficient of the reaction CH₂+H→CH+ H₂ was determined indirectly in the same system: © 1997 John Wiley & Sons, Inc.     

Bacterial Reduction of Chromium

A mixed culture was enriched from surface soil obtained from an eastern United States site highly contaminated with chromate. Growth of the culture was inhibited by a chromium concentration of 12 mg/L. Another mixed culture was enriched from subsurface soil obtained from the Hanford reservation, at the fringe of a chromate plume. The enrichment medium was minimal salts solution augmented with acetate as the carbon source, nitrate as the terminal electron acceptor, and various levels of chromate. This mixed culture exhibited chromate tolerance, but not chromate reduction capability, when growing anaerobically on this medium. However, this culture did exhibit chromate reduction capability when growing anaerobically on TSB. Growth of this culture was not inhibited by a chromium concentration of 12 mg/L. Mixed cultures exhibited decreasing diversity with increasing levels of chromate in the enrichment medium. An in situ bioremediation strategy is suggested for chromate contaminated soil and groundwater.

     

Ein Beitrag über Oxide vom Typ AMO4 (A = Ti3+, Cr3+; M = Nb5+, Ta5+)

A Contribution on Ternary Oxides of the AMO₄-Type (A = Ti³⁺, Cr³⁺; M = Nb⁵⁺, Ta⁵⁺ ) CrNbO₄, CrTaO₄, TiNbO₄, and TiTaO₄ were prepared by CO₂-laser technique. X-ray single crystal investigations show a random distribution of the metal ions in Rutil type structure, space group D–P4₂/mnm. Calculations of the free energy of reaction between Ti₂O₃ and Nb₂O₅ show higher stability of TiO₂ beside NbO₂. In TiNbO₄ both metals exhibit the oxidation state +4.     

New Approach to Model Validation and Fault Diagnosis

The paper presents a new approach to model validation and fault diagnosis problems for a class of uncertain systems in which the uncertainty is described by an integral quadratic constraint. The new approach is developed by applying methods from linear quadratic optimal control theory. This leads to a method for model validation and fault diagnosis which is based around a robust Kalman filter type structure.     

Left versus right canonical Wiener-Hopf factorization and realization

For an arbitrary rational matrix function, not necessarily analytic at infinity, the existence of a right canonical Wiener-Hopf factorization is characterized in terms of a left canonical Wiener-Hopf factorization. Formulas for the factors in a right factorization are given in terms of the formulas for the factors in a given left factorization. All formulas are based on a special representation of a rational matrix function involving a quintet of matrices.     

Comparing branch-and-price algorithms for the Multi-Commodity k-splittable Maximum Flow Problem

The Multi-Commodity k-splittable Maximum Flow Problem consists in routing as much flow as possible through a capacitated network such that each commodity uses at most k paths and the capacities are satisfied. The problem appears in telecommunications, specifically when considering Multi-Protocol Label Switching. The problem has previously been solved to optimality through branch-and-price. In this paper we propose two exact solution methods both based on an alternative decomposition. The two methods differ in their branching strategy. The first method, which branches on forbidden edge sequences, shows some performance difficulty due to large search trees. The second method, which branches on forbidden and forced edge sequences, demonstrates much better performance. The latter also outperforms a leading exact solution method from the literature. Furthermore, a heuristic algorithm is presented. The heuristic is fast and yields good solution values.     

Analyzing continuous state space failure time processes: Two further results*

In a recent paper, Petersen (1988) considered a continuous state space failure time process. The central result provided in that paper was that the destination‐specific rate of transition of the process can be specified in two steps. First, one specifies the overall rate at which a change occurs. Then, one specifies the probability density function of the destination state, given that a transition occurred. This two‐step property was used in deriving the likelihood of the data and was exploited for purposes of estimation. The overall rate of transition can be estimated from the data on durations between changes in the dependent variable. The density for the new value of the dependent variable, given a change, can be estimated from the data on the values of the dependent variable after the change.

This paper extends these results in two ways. First, it is shown that one can derive the likelihood of the process directly from the destination‐specific rate of transition, without going through its decomposition into the overall rate times the density of the destination state, given a transition. Once the likelihood is derived, estimation is comparatively straightforward. Second, it is shown how one can derive, at each point in time, a more standard regression function for the continuous dependent variable, where its value is expressed in terms of its conditional mean plus an error term.