The isomerization equilibrium between cis and trans chloride ruthenium olefin metathesis catalysts from quantum mechanics calculations

The cis-trans chloride isomerization of a ruthenium olefin metathesis catalyst is studied using quantum mechanics (B3LYP DFT), including the Poisson-Boltzmann (PBF) continuum approximation. The predicted geometries agree with experiment. The energies in methylene chloride, lead to DeltaG = -0.70 kcal/mol and a cis:trans ratio of 76:24, quite close to the experimental value of DeltaG = -0.78 kcal/mol or c:t 78:22. In contrast, we predict that in benzene c:t = 4:96 in agreement with the experimental observation of only the trans isomer. Our calculated relative activation energies explain the observed difference in initiation rates and suggest that each isomer should be isolable in high ratio by simply changing solvent.     

Measurement of the Lambda b lifetime in the exclusive decay Lambda b --> J/psi Lambda

We have measured the Lambda b lifetime using the exclusive decay Lambda b --> J/psi Lambda, based on 1.2 fb(-1) of data collected with the D0 detector during 2002-2006. From 171 reconstructed Lambda b decays, where the J/psi and Lambda are identified via the decays J/psi --> mu+ mu- and Lambda --> ppi, we measured the Lambda b lifetime to be tau(Lambda b)=1.218 (+0.130)/(-0.115) (stat) +/- 0.042(syst) ps. We also measured the B0 lifetime in the decay B0 --> J/psi(mu+ mu-)K(0)/(S)(pi+ pi-) to be tau(B0)=1.501 (+0.078)/(-0.074) (stat) +/- 0.050(syst) ps, yielding a lifetime ratio of tau(Lambda b)/tau(B0)=0.811 (+0.096)/(-0.087) (stat) +/- 0.034(syst).     

Search for techniparticles in e+jets events at D0

We search for the technicolor process pp-->rhoT/omegaT-->WpiT in events containing one electron and two jets, in data corresponding to an integrated luminosity of 390 pb(-1), recorded by the D0 experiment at the Fermilab Tevatron. Technicolor predicts that technipions pi(T) decay dominantly into bb, bc, or bc, depending on their charge. In these events b and c quarks are identified by their secondary decay vertices within jets. Two analysis methods based on topological variables are presented. Since no excess above the standard model prediction was found, the result is presented as an exclusion in the pi(T) vs rho(T) mass plane for a given set of model parameters.     

Phosphine-catalyzed annulations of azomethine imines: allene-dependent [3 + 2], [3 + 3], [4 + 3], and [3 + 2 + 3] pathways

In this paper we describe the phosphine-catalyzed [3 + 2], [3 + 3], [4 + 3], and [3 + 2 + 3] annulations of azomethine imines and allenoates. These processes mark the first use of azomethine imines in nucleophilic phosphine catalysis, producing dinitrogen-fused heterocycles, including tetrahydropyrazolo-pyrazolones, -pyridazinones, -diazepinones, and -diazocinones. Counting the two different reaction modes in the [3 + 3] cyclizations, there are five distinct reaction pathways-the choice of which depends on the structure and chemical properties of the allenoate. All reactions are operationally simple and proceed smoothly under mild reaction conditions, affording a broad range of 1,2-dinitrogen-containing heterocycles in moderate to excellent yields. A zwitterionic intermediate formed from a phosphine and two molecules of ethyl 2,3-butadienoate acted as a 1,5-dipole in the annulations of azomethine imines, leading to the [3 + 2 + 3] tetrahydropyrazolo-diazocinone products. The incorporation of two molecules of an allenoate into an eight-membered-ring product represents a new application of this versatile class of molecules in nucleophilic phosphine catalysis. The salient features of this protocol--the facile access to a diverse range of nitrogen-containing heterocycles and the simple preparation of azomethine imine substrates--suggest that it might find extensive applications in heterocycle synthesis.     

Kinetic and mechanistic insight into the thermodynamic degradation of saxagliptin

The dipeptidyl peptidase-IV inhibitor saxagliptin (Onglyza) can undergo a thermodynamically favored cyclization to form the corresponding cyclic amidine. The kinetics and mechanism of this conversion were examined to develop a commercial synthesis that afforded saxagliptin with only trace levels of this key byproduct. Important findings of this work are the identification of a profound solvent effect and the determination of an autocatalytic pathway. Both of these phenomena result from transition structures involving proton transfer.     

A Neumann problem for the KdV equation with Landau damping on a half-line

We consider the initial-boundary value problem on a half-line for the KdV equation with Landau damping. We study traditionally important problems of the theory of nonlinear partial differential equations, such as global in time existence of solutions to the initial-boundary value problem and the asymptotic behavior of solutions for large time.     

Search for pair production of scalar bottom quarks in pp collisions at square root of s = 1.96 TeV

A search for direct production of scalar bottom quarks (b) is performed with 310 pb(-1) of data collected by the D0 experiment in pp collisions at square root s = 1.96 TeV at the Fermilab Tevatron Collider. The topology analyzed consists of two b jets and an imbalance in transverse momentum due to undetected neutralinos (chi(1)0), with chi(1)0 assumed to be the lightest supersymmetric particle. We find the data consistent with standard model expectations, and set a 95% C.L. exclusion domain in the (m(b), m(chi(1)0)) mass plane, improving significantly upon the results from run I of the Tevatron.     

Direct limits on the oscillation frequency

We report results of a study of the B(s)(0) oscillation frequency using a large sample of B(s)(0) semileptonic decays corresponding to approximately 1 fb(-1) of integrated luminosity collected by the D0 experiment at the Fermilab Tevatron Collider in 2002-2006. The amplitude method gives a lower limit on the B(s)(0) oscillation frequency at 14.8 ps(-1) at the 95% C.L. At delta m(s) = 19 ps(-1), the amplitude deviates from the hypothesis A= 0(1) by 2.5 (1.6) standard deviations, corresponding to a two-sided C.L. of 1% (10%). A likelihood scan over the oscillation frequency, delta m(s), gives a most probable value of 19 ps(-1) and a range of 17 < delta m(s) < 21 ps(-1)at the 90% C.L., assuming Gaussian uncertainties. This is the first direct two-sided bound measured by a single experiment. If delta m(s) lies above 22 ps(-1), then the probability that it would produce a likelihood minimum similar to the one observed in the interval 16-22 ps(-1) is (5.0 +/- 0.3)%.     

Role of lipids in urinary stones: studies of calcium oxalate precipitation at phospholipid langmuir monolayers

This article reviews the authors' experiments on calcium oxalate growth at lipid monolayers. Calcium oxalate is the principal mineral component of most urinary stones. Membrane constituents associate either actively or passively with calcific minerals during stone formation, and it has been proposed that lipid assemblies play a significant role, possibly providing sites for the initial nucleation event. Langmuir monolayers allow systematic studies of the heterogeneous precipitation of calcium oxalate at lipid assemblies. The influences of the chemical identity of the lipid headgroup, the organization of the monolayer, and the presence of heterogeneities and phase boundaries within the monolayer have been explored.     

Ab initio multireference configuration-interaction study of hydrogen molecule activation by Cs-promoted Pt clusters

The adsorption of the H2 molecule on CsnPt(5-n) bcc (111) clusters for Cs/Pt rates of 20%, 40%, and 80% is studied using ab initio multiconfigurational self-consistent field plus multireference configuration-interaction variational and perturbative calculations. The H2 interaction with the clusters is studied in ground and excited states with geometry optimization, where the hydrogen adsorption takes place by a Pt atom. These calculations are compared with those of H2 adsorption on Pt4. The most stable configurations of Cs/Pt4 and Cs2Pt3 clusters (Cs/Pt rates of 20% and 40%) are a doublet and a closed-shell singlet, respectively. Both clusters capture and activate the hydrogen molecule and their behaviors resemble Pt4. The H2 capture distances are, respectively, similar and smaller than Pt4 capture distances, while the H-H bond dissociation distances are similar and bigger than those of Pt4; however, none of them presents activation barriers. The most stable Cs4Pt cluster (Cs/Pt rate of 80%) is also a closed-shell singlet; it also captures and activates the hydrogen molecule and shows a different behavior as compared with Cs/Pt4, Cs2Pt3, and Pt4 clusters. The capture distance is quite smaller and is obtained after surmounting an activation barrier. For all clusters studied here, no hydrogen absorption was observed, only the adsorption of H2.