Random continued fractions and inverse Gaussian distribution on a symmetric cone

In this paper we introduce the inverse Gaussian and Wishart distributions on the cone of real (n, n) symmetric positive definite matricesH _n ⁺ () and more generally on an irreducible symmetric coneC. Then we study the convergence of random continued fractions onH _n ⁺ () andC by means of real Lagrangians forH _n ⁺ () and by new algebraic identities on symmetric cones forC. Finally we get a characterization of the inverse Gaussian distribution onH _n ⁺ () andC.     

Bisphosphonate prodrugs: synthesis of new aromatic and aliphatic 1-hydroxy-1,1-bisphosphonate partial esters

Methods for the preparation of various 1-hydroxy-1,1-bisphosphonate partial esters were developed. They were obtained from (alkyl or phenyl) bis(trimethylsilyl) phosphite and aromatic or aliphatic acid chlorides, followed by methanolysis.     

Total synthesis of the marine pyridoacridine alkaloid sebastianine A

The synthesis of the marine alkaloid sebastianine A and of a regioisomer has been accomplished via hetero-Diels-Alder reaction of indole-4,7-dione or N-tosylindole-4,7-dione with trifluoroacetamidocinnamaldehyde dimethylhydrazone, and subsequent cyclisation in alkaline conditions.     

Synthesis of tailor-made glycoconjugate mimetics of heparan sulfate that bind IFN-gamma in the nanomolar range

We have recently described the preparation of three building blocks for the combinatorial synthesis of heparan sulfate (HS) fragments. Herein we show that one of these building blocks (disaccharide 4) allows the preparation, in high yields and with total alpha stereoselectivity, of tetra-, hexa- and octasaccharides from the heparin (HP) regular region, by using 2+2, 2+4 and 4+4 glycosylation strategies, respectively. These oligosaccharides were processed into sulfated derivatives bearing an allyl moiety in the anomeric position. The UV-promoted conjugation of these compounds with alpha,omega-bis(thio)poly(ethylene glycol) spacers of three different lengths allowed us to prepare nine benzylated glycoconjugates. After final deprotection, the glycoconjugates 1 a-c, 2 a-c and 3 a-c were obtained and their ability to inhibit the interaction between IFN-gamma and HP was tested by using surface plasmon resonance detection. Compound 3 b, containing two HP octasaccharides linked by a 50-A linker was able to inhibit the IFN-gamma/HP interaction with an IC(50) value of approximately 35 nM. In addition, the nine glycoconjugates were perfect tools in the study to ascertain the topology of the IFN-gamma binding site on HS. Compounds 1 a-c, 2 a-c and 3 a-c, by mimicking the alternating sulfated and nonsulfated regions found in HS, thus comprise the first example of a library of synthetic HS mimetics giving access to the "second level of molecular diversity" found in HS.     

Chiral Phosphate in Rhodium‐Catalyzed Asymmetric [2+2+2] Cycloaddition: Ligand,Counterion, or Both?

Investigations based on NMR spectroscopy, mass spectrometry, and DFT calculations shed light on the metallic species generated in the rhodium‐catalyzed asymmetric [2+2+2] cycloaddition reaction between diynes and isocyanates with the chiral phosphate TRIP. The catalytic mixture comprising [{Rh(cod)Cl}₂], 1,4‐diphenylphosphinobutane (dppb), and Ag(S)‐TRIP actually gives rise to two species, both having an effect on the stereoselectivity. One is a rhodium(I) complex in which TRIP is a weakly coordinating counterion, whereas the other is a bimetallic Rh/Ag complex in which TRIP is a strongly coordinating X‐type ligand.     

An hp‐adaptive unstructured finite volume solver for compressible flows

The idea of hp‐adaptation, which has originally been developed for compact schemes (such as finite element methods), suggests an adaptation scheme using a mixture of mesh refinement and order enrichment based on the smoothness of the solution to obtain an accurate solution efficiently. In this paper, we develop an hp‐adaptation framework for unstructured finite volume methods using residual‐based and adjoint‐based error indicators. For the residual‐based error indicator, we use a higher‐order discrete operator to estimate the truncation error, whereas this estimate is weighted by the solution of the discrete adjoint problem for an output of interest to form the adaptation indicator for adjoint‐based adaptations. We perform our adaptation by local subdivision of cells with nonconforming interfaces allowed and local reconstruction of higher‐order polynomials for solution approximations. We present our results for two‐dimensional compressible flow problems including subsonic inviscid, transonic inviscid, and subsonic laminar flow around the NACA 0012 airfoil and also turbulent flow over a flat plate. Our numerical results suggest the efficiency and accuracy advantages of adjoint‐based hp‐adaptations over uniform refinement and also over residual‐based adaptation for flows with and without singularities.     

Terminal Deoxy Hydroxyamino Sugars

Abstract

Reduction of sugar aldoximes gave in good yield the corresponding terminal deoxy hydroxyamino sugars. These compounds were found to be reasonably stable (they could be kept for some weeks at 4° C). On standing in the air, these compounds in solution were spontaneously oxidized to the corresponding nitroxide free radicals whose ESR spectra gave useful structural information.     

High‐performance liquid chromatographic method for the quantification of Mitragyna inermis alkaloids in order to perform pharmacokinetic studies

In Africa, Mitragyna inermis (Willd.) O. Kuntze (Rubiaceae) is commonly used in traditional medicine to treat malaria. Antimalarial activity is mostly due to the hydromethanolic extract of M. inermis leaves and especially to the main alkaloids, uncarine D and isorhynchophilline. In the present study, we describe for the first time an HPLC method for the simultaneous quantification of uncarine D and isorhynchophylline in biological matrices. SPE was used to extract the components and the internal standard naphthalene from human and pig plasma samples. Chromatographic separation was performed on a C‐18 reversed column at a flow rate of 1 mL/min, using methanol–phosphate buffer (10:90, pH 7), as a mobile phase. Good linearity was observed over the concentration ranges of 0.0662–3.31 μg/mL for uncarine D and 0.0476–2.38 μg/mL for isorynchophylline. The precision was less than 12% and the accuracy was from 86 to 107% without any discrepancy between the two species. Uncarine D and isorhynchophylline recoveries were over 80%. These results allowed the quantification of both uncarine D and isorhynchophylline in pig plasma after intravenous administration of M. inermis extract.     

Trifluoromethyl radical triggered radical cyclization of N-benzoyl ynamides leading to isoindolinones

Science China Chemistry - Under photocatalytic reductive conditions, trifluoromethyl radical addition onto an ynamide followed by cyclization on a benzoyl moiety produces diverse isoindolinone...