Computation of free energy profiles with parallel adaptive dynamics

We propose a formulation of adaptive computation of free energy differences, in the ABF or nonequilibrium metadynamics spirit, using conditional distributions of samples of configurations which evolve in time. This allows to present a truly unifying framework for these methods, and to prove convergence results for certain classes of algorithms. From a numerical viewpoint, a parallel implementation of these methods is very natural, the replicas interacting through the reconstructed free energy. We show how to improve this parallel implementation by resorting to some selection mechanism on the replicas. This is illustrated by computations on a model system of conformational changes.Comment: 4 pages, 1 Figur

The targeting of zero-rated basic foodstuffs under value-added tax (VAT) in South Africa

Since the inception of VAT in South Africa, various studies have been conducted to investigate the distributional impact of the tax as well as the effectiveness of zero-rating as tool to alleviate the burden on poor households. This paper argues that the targeting of the zero-rated basket can be improved to enhance the intended equity gain. Using the food category of vegetables as a case study, and distinguishing between sub-groups of vegetables, this paper conducts tax incidence analyses to compare the relative burden of VAT on different categories of vegetables for various income groups. The findings suggest that canned vegetables should be included in the zero-rated basket, frozen vegetables should remain zero-rated, but some (not ‘basic’) fresh vegetables should be taxed at the standard rate. It also strongly suggests that the specific items in the zero-rated basket should be reviewed on a regular basis.Department of HE and Training approved lis

Synthesis and exploration of electronically modified (R)-5,5-dimethyl-(p-CF_3)_3-i-PrPHOX in palladium-catalyzed enantio- and diastereoselective allylic alkylation: a practical alternative to (R)-(p-CF_3)_3-t-BuPHOX

The synthesis of the novel electronically modified phosphinooxazoline (PHOX) ligand, (R)-5,5-dimethyl-(p-CF_3)_3-i-PrPHOX, is described. The utility of this PHOX ligand is explored in both enantio- and diastereoselective palladium-catalyzed allylic alkylations. These investigations prove (R)-5,5-dimethyl-(p-CF_3)_3-i-PrPHOX to be an effective and cost-efficient alternative to electronically modified PHOX ligands derived from the prohibitively expensive (R)-t-leucine

The Total Synthesis of (–)-Scabrolide A

The first total synthesis of the norcembranoid diterpenoid scabrolide A is disclosed. The route begins with the synthesis of two chiral pool-derived fragments, which undergo a convergent coupling to expediently introduce all 19 carbon atoms of the natural product. An intramolecular Diels–Alder reaction and an enone–olefin cycloaddition/fragmentation sequence are then employed to construct the fused [5–6–7] linear carbocyclic core of the molecule and complete the total synthesis

Proposed system safety design and test requirements for the microlaser ordnance system

Safety for pyrotechnic ignition systems is becoming a major concern for the military. In the past twenty years, stray electromagnetic fields have steadily increased during peacetime training missions and have dramatically increased during battlefield missions. Almost all of the ordnance systems in use today depend on an electrical bridgewire for ignition. Unfortunately, the bridgewire is the cause of the majority of failure modes. The common failure modes include the following: broken bridgewires; transient RF power, which induces bridgewire heating; and cold temperatures, which contracts the explosive mix away from the bridgewire. Finding solutions for these failure modes is driving the costs of pyrotechnic systems up. For example, analyses are performed to verify that the system in the environment will not see more energy than 20 dB below the 'No-fire' level. Range surveys are performed to determine the operational, storage, and transportation RF environments. Cryogenic tests are performed to verify the bridgewire to mix interface. System requirements call for 'last minute installation,' 'continuity checks after installation,' and rotating safety devices to 'interrupt the explosive train.' As an alternative, MDESC has developed a new approach based upon our enabling laser diode technology. We believe that Microlaser initiated ordnance offers a unique solution to the bridgewire safety concerns. For this presentation, we will address, from a system safety viewpoint, the safety design and the test requirements for a Microlaser ordnance system. We will also review how this system could be compliant to MIL-STD-1576 and DOD-83578A and the additional necessary requirements

A reduced model for shock and detonation waves. II. The reactive case

We present a mesoscopic model for reactive shock waves, which extends a previous model proposed in [G. Stoltz, Europhys. Lett. 76 (2006), 849]. A complex molecule (or a group of molecules) is replaced by a single mesoparticle, evolving according to some Dissipative Particle Dynamics. Chemical reactions can be handled in a mean way by considering an additional variable per particle describing a rate of reaction. The evolution of this rate is governed by the kinetics of a reversible exothermic reaction. Numerical results give profiles in qualitative agreement with all-atom studies

A Synthetic Strategy toward Eight-Membered Cyclic Amines by Cycloetherification and Claisen Rearrangement

Eight-membered nitrogen-containing heterocycles were straightforwardly produced by a nickel-catalyzed cycloetherification and subsequent Claisen rearrangement of secondary and tertiary alcohols. In particular, a one-pot transformation was achieved with tertiary alcohols in moderate to good yields. This operationally simple reaction is tolerant of many functional groups and applicable to the synthesis of various medium-sized ring nitrogen-containing heterocycles