Enantioselective Synthesis and Racemization of (−)-Sinoracutine

Sinoracutine is a recently isolated alkaloid with unusual stereochemical and biological properties. It features an unprecedented tetracyclic 6/6/5/5 skeleton that bears an N-methylpyrrolidine ring fused to a cyclopentenone. Interestingly, both enantiomers of sinoracutine have been independently isolated from the same plant, yet the molecule does not appear to occur as a racemate. Here, we present a short synthesis of (−)-sinoracutine that relies on a highly diastereoselective Pauson–Khand reaction and a Mandai–Claisen reaction to install the quaternary stereocenter. Our work establishes the absolute configuration of the levorotatory isomer and suggests that the optical purity of sinoracutine varies in nature due to its gradual racemization. Experimental evidence supports this proposal, and a plausible mechanism for the racemization is provided.     

Measurement of the Lambdab0 lifetime using semileptonic decays

We report a measurement of the Lambda(b)(0) lifetime using a sample corresponding to 1.3 fb(-1) of data collected by the D0 experiment in 2002-2006 during run II of the Fermilab Tevatron collider. The Lambda(b)(0) baryon is reconstructed via the decay Lambda(b)(0)-->micronuLambda(c)(+)X. Using 4437+/-329 signal candidates, we measure the Lambda(b)(0) lifetime to be tau(Lambda(b)(0))=1.290(-0.110)(+0.119)(stat)(-0.091)(+0.087)(syst) ps, which is among the most precise measurements in semileptonic Lambda(b)(0) decays. This result is in good agreement with the world average value.     

Properties of L=1 B(1) and B(2)* mesons

This Letter presents the first strong evidence for the resolution of the excited B mesons B(1) and B(2)* as two separate states in fully reconstructed decays to B(+)(*)pi(-). The mass of B(1) is measured to be 5720.6+/-2.4+/-1.4 MeV/c(2) and the mass difference DeltaM between B(2)* and B(1) is 26.2+/-3.1+/-0.9 MeV/c;{2}, giving the mass of the B(2)* as 5746.8+/-2.4+/-1.7 MeV/c(2). The production rate for B(1) and B(2)* mesons is determined to be a fraction (13.9+/-1.9+/-3.2)% of the production rate of the B+ meson.     

A GPU-based incompressible Navier–Stokes solver on moving overset grids

In pursuit of obtaining high fidelity solutions to the fluid flow equations in a short span of time, graphics processing units (GPUs) which were originally intended for gaming applications are currently being used to accelerate computational fluid dynamics (CFD) codes. With a high peak throughput of about 1 TFLOPS on a PC, GPUs seem to be favourable for many high-resolution computations. One such computation that involves a lot of number crunching is computing time accurate flow solutions past moving bodies. The aim of the present paper is thus to discuss the development of a flow solver on unstructured and overset grids and its implementation on GPUs. In its present form, the flow solver solves the incompressible fluid flow equations on unstructured/hybrid/overset grids using a fully implicit projection method. The resulting discretised equations are solved using a matrix-free Krylov solver using several GPU kernels such as gradient, Laplacian and reduction. Some of the simple arithmetic vector calculations are implemented using the CU++: An Object Oriented Framework for Computational Fluid Dynamics Applications using Graphics Processing Units, Journal of Supercomputing, 2013, doi:10.1007/s11227-013-0985-9 approach where GPU kernels are automatically generated at compile time. Results are presented for two- and three-dimensional computations on static and moving grids.     

Large Eddy Simulation composition equations for single-phase and two-phase fully multicomponent flows

The Large Eddy Simulation (LES) equations for multicomponent (MC) fuel single-phase (SP) flow and two-phase (TP) flow with phase change are derived from the Direct Numerical Simulation (DNS) equations by filtering the DNS equations using a top-hat filter. Additional to the equations solved for single-component (SC) fuels, composition equations enter the formulation. The species composition is represented through a Probability Distribution Function (PDF), and DNS equations for the PDF moments are solved to find the composition. The TP filtered equations contain three categories of subgrid-scale (SGS) terms: (1) SGS–flux terms, (2) filtered source terms (FSTs) and (3) terms representing the ‘LES assumptions’. For SP flows no FSTs exist. The SGS terms in the LES equations must be either shown negligible or modeled. It is shown that for the composition equations, two equivalent forms of the DNS equations lead to two non-equivalent forms of the LES equations. Criteria are proposed to select the form best suited for LES. These criteria are used in conjunction with evaluations based on a DNS database portraying mixing and phase change, and lead to choosing one of the LES forms which satisfies all criteria. It is shown that the LES assumptions lead to additional SGS terms which require modeling. Further considerations are made for reactive flows.     

Synthesis of antiproliferative Cephalotaxus esters and their evaluation against several human hematopoietic and solid tumor cell lines: uncovering differential susceptibilities to multidrug resistance

Deoxyharringtonine (2), homoharringtonine (3), homodeoxyharringtonine (4), and anhydroharringtonine (5) are reported to be among the most potent members of the antileukemia alkaloids isolated from the Cephalotaxus genus. Convergent syntheses of these four natural products are described, each involving novel synthetic methods and strategies. These syntheses enabled evaluation of several advanced natural and non-natural compounds against an array of human hematopoietic and solid tumor cells. Potent cytotoxicity was observed in several cell lines previously not challenged with these alkaloids. Variations in the structure of the ester chain within this family of alkaloids confer differing activity profiles against vincristine-resistant HL-60/RV+, signalling new avenues for molecular design of these natural products to combat multi-drug resistance.     

Reactivity of Diphosphene towards Oxygen and Diazo Derivatives: New Method of Obtaining Stable Diphosphiranes

Abstract

Different aspects of the reactivity of the diphosphene are presented: reactivity of the lone pair and/or reactivity of the double bond.     

Improving the performance of UDE-based controller using a new filter design

Robust control of uncertain systems has been a field of active research and the technique of uncertainty and disturbance estimator (UDE) has proved itself as a viable tool in the design of a robust control strategy for systems having uncertainties and acted upon by disturbances. Though the technique is quite efficient for ensuring robustness under slow-varying disturbances, the presence of steady-state tracking and estimation errors cannot be ruled out for fast-varying or sinusoidal disturbances. To address this issue, a new form of filter in UDE-based controller is proposed in this work and it is shown that the errors can be kept within acceptable limits by means of appropriate choice of the design parameter \(\alpha \) . Closed-loop stability and simulation results for wing-rock motion control problem employing an UDE-based controller using the new filter are carried out to demonstrate its efficacy against fast-varying uncertainties and disturbances.