Discodermolide/Dictyostatin hybrids: synthesis and biological evaluation

[structure: see text] Two hybrid analogues of discodermolide and dictyostatin (3, 26) have been designed and synthesized. These are the first macrocyclic analogues of discodermolide and biological activities were evaluated and compared with linear discodermolide analogues.     

Multiple one-electron oxidation and reduction of trinuclear bis(2,4-pentanedionato)ruthenium complexes with substituted diquinoxalino[2,3-a:2′,3′-c]phenazine ligands

The complexes (μ₃-L¹/L²)[Ru(acac)₂]₃, acac⁻ = 2,4-pentanedionato, L¹ = 2,3,8,9,14,15-hexachlorodiquinoxalino[2,3-a:2′,3′-c]phenazine and L² = 2,3,8,9,14,15- hexamethyldiquinoxalino[2,3-a:2′,3′-c]phenazine, undergo stepwise one-electron oxidation involving a total of three electrons and stepwise one-electron reduction with three (L²) or four electrons (L¹). All reversibly accessible states were characterized by UV–Vis–NIR spectroelectrochemistry. Oxidation leads to mixed-valent intermediates {(μ₃-L)[Ru(acac)₂]₃}⁺ and {(μ₃-L)[Ru(acac)₂]₃}²⁺ of which the Ru^IIIRu^IIRu^II combinations exhibit higher comproportionation constants K_c than the Ru^IIIRu^IIIRu^II states – in contrast to a previous report for the unsubstituted parent systems {(μ₃-L³)[Ru(acac)₂]₃}^+/2+, L³ = diquinoxalino[2,3-a:2′,3′-c]phenazine. No conspicuous inter-valence charge transfer absorptions were observed for the mixed-valent intermediates in the visible to near-infrared regions. The monocations and monoanions were characterized by EPR spectroscopy, revealing rhombic ruthenium(III) type signals for the former. Electron addition produces ruthenium(II) complexes of the reduced forms of the ligands L, a high resolution EPR spectrum with ¹⁴N and ^35,37Cl hyperfine coupling and negligible g anisotropy was found for {(μ₃-L¹)[Ru(acac)₂]₃}⁻. DFT calculations of (μ₃-L¹)[Ru(acac)₂]₃ confirm several ligand-centered low-lying unoccupied MOs for reduction and several metal-based high-lying occupied MOs for electron withdrawal, resulting in low-energy metal-to-ligand charge transfer (MLCT) transitions.     

Determination of hexavalent chromium by on-line dialysis ion chromatography in a matrix of strong colourants and trivalent chromium

Hexavalent chromium detection in the presence of a high load of colourants without any false positive and in-procedure oxidation of Cr(III) is an important area of study. Colourants are a class of interfering substances in many spectroscopic analyses and chromatographic separations and detection. A purification method using an on-line dialysis technique for ion chromatography (IC) has been developed to remove water-soluble anionic dyes and particulate colourants and other substances to facilitate Cr(VI) quantification and the method is discussed. The dialysis was optimized with Cr(VI) standard solutions for quantification. The efficacy of the procedure for the removal of anionic dyes and detection of Cr(VI) was checked with a Cr(VI) spiked synthetic preparation containing a water-soluble dye and trivalent chromium. Soluble Cr(VI) extracted with organic dyes from environmental samples was analyzed. The method has a detection limit of 5 microg/l, recovery rate of 100% and analysis time less than 20 min.     

Neutral strange particle correlations in 360 GeV/cpp interactions

Production properties and correlations forK _s ⁰ K _s ⁰ ,K _s ⁰ Λ,K _s ⁰ ¯Λ and Λ¯Λ systems in 360 GeV/cpp interactions are presented. All rapidity gap distributions are observed to peak at Δy=0 and the azimuthal angular distributions between the two particles are consistent with being flat. Experimental results are compared with the quark fusion and Lund models of particle production.     

Novel,short, stereospecific synthesis of lyxo-(2R,3R,4R)-phytosphingosine and erythro-(2R,3S)-sphingosine

Lyxo-phytosphingosine and erythro-sphingosine have been elaborated from a common intermediate. The key step in the reaction sequence involves stereo- and regiospecific functionalization of an olefin by intramolecular nucleophilic sulfinyl group participation.     

Performance analysis of extended surfaces subjected to fouling

 The time dependent performance of extended surfaces subjected to fouling is addressed in this work. Where fins are used for augmenting boiling heat transfer, the interaction of local values of temperature excess, fouling resistance and surface characteristics of the deposit can be quite complex. Taking typical asymptotic fouling growth parameters from literature for reverse solubility salts, three kinds of fin geometry are analysed – rectangular, triangular and annular. For various values of the fin parameter mL, the temperature distribution and variation of fouling resistance are obtained as a function of time. To interpret the performance of a fouled fin, a new term `cleanliness efficiency' is introduced. The necessity of choosing an optimal value of mL for the fin is also highlighted here. It is shown that for all three fin configurations, cleanliness efficiency differs little, thus simplifying the geometry dependence. The approach set out in this work will help in the design of finned heat exchangers subjected to fouling and thereby minimise their overdesign. Received on 12 July 2000     

Two-particle correlations in 360 GeV/cp p interactions

Two particle correlations of hadrons produced in 360 GeV/cpp interactions are investigated in the transverse plane and in rapidity. The data were obtained at the European hybrid spectrometer equipped with a rapid cycling bubble chamber. The observed transverse and rapidity correlations are compared with the one string LUND-and a two string dual parton-model. These models predict in general stronger correlations in the transverse plane and much weaker correlations in rapidity than found in the data. The LUND-FRITIOF-and multichain dual parton models provide a better reproduction of the data, although the agreement is not yet satisfactory. Only the UA5 cluster model GENCL shows agreement with the data.     

Chemical-electrochemical method for the determination of the positions of coupling in the dimeric one-electron reduction products of ring-substitued 1-alkylpyridinium ions

A previously described procedure for the determination of the positions of coupling in the dimeric one-electron reduction products of 1-alkylpyridinium ions has been extended to the examination of the coupling positions in the dimeric species resulting from one-electron reduction of ring-substituted 1-alkylpyridinium ions.     

Strategy for purifying maltose binding protein fusion proteins by affinity precipitation

The maltose binding protein (MBP) affinity tag has been extensively used for protein purification. A commercial grade cationic starch could precipitate MBP or an MBP-tagged protein quantitatively by simultaneous addition of 10% (w/v) polyethylene glycol (PEG) and 50 mM calcium chloride. The precipitated MBP or MBP-tagged protein could be selectively dissociated by suspending the precipitate in 1 M NaCl. In the case of a soluble MBP fusion with a fragment of human immunodeficiency virus protein gp120, 38% of the contaminating proteins could be removed by precipitation with PEG/CaCl(2) and 100% of the fusion protein was recovered. In all cases, the purified proteins showed a single band on sodium dodecyl sulfate-polyacrylamide gel electrophoresis and the expected changes in fluorescence emission spectra upon binding to maltose.