Towards the total synthesis of amphidinolide E: an enantioselective synthesis of C12-C29 fragment

An enantioselective synthesis of the C12-C29 fragment of amphidinolide E is described. Key transformations include an intramolecular mercuriocyclization reaction, stereoselective introduction of methyl group at the C2 position, and Stille coupling for the introduction of the diene side chain.     

From D-glucose to biologically potent L-hexose derivatives: synthesis of alpha-L-iduronidase fluorogenic detector and the disaccharide moieties of bleomycin A2 and heparan sulfate

A novel and convenient route for the synthesis of biologically potent and rare L-hexose derivatives from D-glucose is described. Conversion of diacetone-alpha-D-glucose (14) into 1,2:3,5-di-O-isopropylidene-beta-L-idofuranose (19) was efficiently carried out in two steps. Orthogonal isopropylidene rearrangement of compound 19 led to 1,2:5,6-di-O-isopropylidene-beta-L-idofuranose (27), which underwent regioselective epimerization at the C3 position to give the L-talo- and 3-functionalized L-idofuranosyl derivatives. Hydrolysis of compound 19 under acidic conditions furnished 1,6-anhydro-beta-L-idopyranose (35) in excellent yield, which was successfully transformed into the corresponding L-allo, L-altro, L-gulo, and L-ido derivatives via regioselective benzylation, benzoylation, triflation and nucleophilic substitution as the key steps. Applications of these 1,6-anhydro-beta-L-hexopyranoses as valuable building blocks to the syntheses of 4-methylcoumarin-7-yl-alpha-L-iduronic acid and the disaccharide moieties of bleomycin A(2) as well as heparan sulfate are highlighted.     

Synthetic studies toward macrocidins: an RCM approach for the construction of the central cyclic core

The central macrocyclic core of the macrocidins was constructed using RCM as the key reaction. A preliminary investigation dealing with the key reactions, that is, the Dieckmann cyclization and the RCM, revealed that RCM of the β-ketoamide is better than RCM of the corresponding acyltetramic acid.     

Bounds tightening based on optimality conditions for nonconvex box-constrained optimization

First-order optimality conditions have been extensively studied for the development of algorithms for identifying locally optimal solutions. In this work, we propose two novel methods that directly exploit these conditions to expedite the solution of box-constrained global optimization problems. These methods carry out domain reduction by application of bounds tightening methods on optimality conditions. This scheme is implicit and avoids explicit generation of optimality conditions through symbolic differentation, which can be memory and time intensive. The proposed bounds tightening methods are implemented in the global solver BARON. Computational results on a test library of 327 problems demonstrate the value of our proposed approach in reducing the computational time and number of nodes required to solve these problems to global optimality.     

Assessment of natural uranium and 226Ra concentration in ground water around the uranium mine at Narwapahar, Jharkhand, India and its radiological significance

A brief study on dissolved radionuclides in aquatic environment, especially in ground water, constitutes the key aspect for assessment and control of natural exposure. In the present study the distribution of natural uranium and ²²⁶Ra concentration were measured in ground water samples collected within a 10 km radius around the Narwapahar uranium mine in the Singhbhum thrust belt of Jharkhand, India in 2007–2008. The natural uranium content in the ground water samples in this region was found to vary from 0.1 to 3.75 μg L^?1 with an average of 0.87 ± 0.73 μg L^?1 and ²²⁶Ra concentration was found to vary from 5.2 to 38.1 mBq L^?1 with an average of 13.73 ± 7.34 mBq L^?1. The mean annual ingestion dose due to intake of natural uranium and ²²⁶Ra through drinking water pathway to male and female adults population was estimated to be 6.55 and 4.78 μSv y^?1, respectively, which constitutes merely a small fraction of the reference dose level of 100 μSv y^?1 as recommended by WHO.     

Unusual monodentate binding mode of 2,2'-dipyridylamine (L) in isomeric trans-(acac)2RuII(L)2, trans-[(acac)2RuIII(L)2]ClO4, and cis-(acac)2RuII(L)2 (acac = acetylacetonate). synthesis, structures, and spectroscopic, electrochemical, and magnetic aspects

The reaction of cis-Ru(acac)2(CH3CN)2 (acac = acetylacetonate) with 2,2'-dipyridylamine (L) in ethanolic medium resulted in facile one-pot synthesis of stable [(acac)2RuIII(L)]ClO4 ([1]ClO4), trans-[(acac)2RuII(L)2] (2), trans-[(acac)2RuIII)L)2]ClO4 ([2]ClO4), and cis-[(acac)2RuII(L)2] (3). The bivalent congener 1 was generated via electrochemical reduction of [1]ClO4. Although in [1]+ the dipyridylamine ligand (L) is bonded to the metal ion in usual bidentate fashion, in 2/[2]+ and 3, the unusual monodentate binding mode of L has been preferentially stabilized. Moreover, in 2/[2]+ and 3, two such monodentate L's have been oriented in the trans- and cis-configurations, respectively. The binding mode of L and the isomeric geometries of the complexes were established by their single-crystal X-ray structures. The redox stability of the Ru(II) state follows the order 1 < 2 < 3. In contrast to the magnetic moment obtained for [1]ClO4, mu = 1.84 muB at 298 K, typical for low-spin Ru(III) species, the compound [2]ClO4 exhibited an anomalous magnetic moment of 2.71 muB at 300 K in the solid state. The variable-temperature magnetic measurements showed a pronounced decrease of the magnetic moment with the temperature, and that dropped to 1.59 muB at 3 K. The experimental data can be fitted satisfactorily using eq 2 that considered nonquenched spin-orbit coupling and Weiss constant in addition to the temperature-independent paramagnetism. [1]ClO4 and [2]ClO4 displayed rhombic and axial EPR spectra, respectively, in both the solid and the solution states at 77 K.     

A hybrid FVM–LBM method for single and multi‐fluid compressible flow problems

The lattice Boltzmann method (LBM) has established itself as an alternative approach to solve the fluid flow equations. In this work we combine LBM with the conventional finite volume method (FVM), and propose a non‐iterative hybrid method for the simulation of compressible flows. LBM is used to calculate the inter‐cell face fluxes and FVM is used to calculate the node parameters. The hybrid method is benchmarked for several one‐dimensional and two‐dimensional test cases. The results obtained by the hybrid method show a steeper and more accurate shock profile as compared with the results obtained by the widely used Godunov scheme or by a representative flux vector splitting scheme. Additional features of the proposed scheme are that it can be implemented on a non‐uniform grid, study of multi‐fluid problems is possible, and it is easily extendable to multi‐dimensions. These features have been demonstrated in this work. The proposed method is therefore robust and can possibly be applied to a variety of compressible flow situations. Copyright © 2009 John Wiley & Sons, Ltd.