Selective determination of mono- and dihydroxylated analogs of polybrominated diphenyl ethers in marine sponges by liquid-chromatography tandem mass spectrometry

A number of bioactive brominated secondary metabolites, including hydroxylated polybrominated diphenyl ethers, have been isolated from algae, sponges, and bacteria. In the present study, a screening method using liquid-chromatography tandem mass spectrometry was developed for the identification and selective determination of dihydroxy (diOH), hydroxy-methoxy (OH-MeO), and dimethoxy (diMeO) analogs of tetra- to hexa-BDEs in marine biota. In negative atmospheric pressure chemical ionization (APCI) mode, diOH and OH-MeO analogs provided intense [M-H](-) ions, whereas diMeO analogs provided characteristic [M-Br+O](-) and [M-CH(3)](-) ions. This enabled the diOH-, OH-MeO-, and diMeO-PBDEs to be distinguished using selected reaction monitoring transitions in the APCI source. Recoveries of 2'-OH-6-MeO-2,3',4,5'-tetra-BDE in spiked marine samples were 84 ± 5 %, with a limit of quantification at 9.1 ng mL(-1) (signal-to-noise ratio = 10). The developed method was used to analyze two sponge species collected from Palau, Micronesia; the concentration ratio of diOH-tetra-BDE:OH-MeO-tetra-BDE was 10:1 for the Lamellodysidea sp., whereas it was 1:30 for the Callyspongia sp.     

Crystal Growth,Structure, and Magnetic Properties of a Two‐dimensional Triangular Lattice Magnet,Cu2(OH)3HCO2

We prepared single crystals of basic copper formate Cu₂(OH)₃HCO₂ ( 1) by hydrolysis of formate anions in an aqueous solution of copper formate. X‐ray structure analysis showed that this material has a two‐dimensional triangular lattice network with S=1/2. The temperature dependence of magnetic susceptibility revealed antiferromagnetic ordering at 5.4 K. A spin‐flop transition was observed at about 20 kOe at 2 K, thereby indicating metamagnetic‐like behavior. The saturation magnetization was almost one‐half of the theoretical value at 2 K under 70 kOe. The magnetic behaviors of 1 were also discussed with regard to its crystal structure. The preparation method presented herein is convenient and available for single crystal growth of metal hydroxide derivatives with various anions.     

Experimental visualization of lithium conduction pathways in garnet-type Li(7)La(3)Zr(2)O(12)

The evolution of the Li-ion displacements in the 3D interstitial pathways of the cubic garnet-type Li(7)La(3)Zr(2)O(12), cubic Li(7)La(3)Zr(2)O(12), was investigated with high-temperature neutron diffraction (HTND) from RT to 600 °C; the maximum-entropy method (MEM) was applied to estimate the Li nuclear-density distribution. Temperature-driven Li displacements were observed; the displacements indicate that the conduction pathways in the garnet framework are restricted to diffusion through the tetrahedral sites of the interstitial space.     

On-target separation of analyte with 3-aminoquinoline/α-cyano-4-hydroxycinnamic acid liquid matrix for matrix-assisted laser desorption/ionization mass spectrometry

3-Aminoquinoline/α-cyano-4-hydroxycinnamic acid (3AQ/CHCA) is a liquid matrix (LM), which was reported by Kumar et al. in 1996 for matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. It is a viscous liquid and has some advantages of durability of ion generation by a self-healing surface and quantitative performance. In this study, we found a novel aspect of 3AQ/CHCA as a MALDI matrix, which converges hydrophilic material into the center of the droplet of analyte-3AQ/CHCA mixture on a MALDI sample target well during the process of evaporation of water derived from analyte solvent. This feature made it possible to separate not only the buffer components, but also the peptides and oligosaccharides from one another within 3AQ/CHCA. The MALDI imaging analyses of the analyte-3AQ/CHCA droplet indicated that the oligosaccharides and the peptides were distributed in the center and in the whole area around the center of 3AQ/CHCA, respectively. This 'on-target separation' effect was also applicable to glycoprotein digests such as ribonuclease B. These features of 3AQ/CHCA liquid matrix eliminate the requirement for pretreatment, and reduce sample handling losses thus resulting in the improvement of throughput and sensitivity.     

Bezout equations over bivariate polynomial matrices related by an entire function

This study addresses Bezout equations over bivariate polynomial matrices, where the relationship between two variables is described by a real entire function. This paper proposes a solution method that makes optimal use of minor primeness to reduce such Bezout equations to simple equations over univariate scalar polynomials. The proposed solution method requires only matrix calculations, thus making it very useful, especially in the absence of modern computer algebra systems.     

Achiral benzophenone ligand-rhodium complex with chiral diamine activator for high enantiocontrol in asymmetric transfer hydrogenation

The chirality of an achiral benzophenone-based rhodium complex can be controlled by chiral diamines to afford significantly high enantioselectivity in the catalytic asymmetric transfer hydrogenation of ketones (up to 99% ee, 99% yield).     

Total synthesis and biological evaluation of neodysiherbaine A and analogues

Dysiherbaine (1) and its congener neodysiherbaine A (2) are naturally occurring excitatory amino acids with selective and potent agonistic activity for ionotropic glutamate receptors. We describe herein the total synthesis of 2 and its structural analogues 3-8. Advanced key intermediate 16 was employed as a branching point to assemble a series of these analogues 3-8 with respect to the C8 and C9 functionalities, which would not have been accessible through manipulations of the natural product itself. The synthesis of key intermediate 16 features (i) stereocontrolled C-glycosylation to set the C6 stereocenter, (ii) concise synthesis of the bicyclic ether skeleton through chemo- and stereoselective dihydroxylation of the exo-olefin and stereoselective epoxidation of the endo-olefin, followed by epoxide ring opening/5-exo ring closure, and (iii) catalytic asymmetric hydrogenation of enamide ester to construct the amino acid appendage. A preliminary biological evaluation of analogues for their in vivo toxicity against mice and binding affinity for glutamate receptors showed that both the type and stereochemistry of the C8 and C9 functional groups affected the subtype selectivity of dysiherbaine analogues for members of the kainic acid receptor family.     

Synthesis of 2′,3′-dideoxynucleosides via C-S bond cleavage: N-glycosylation of 2,3-dideoxy-1-[(2-pyridylmethyl)thio]glycoside

N-Glycosylation of 2,3-dideoxy-1-[(2-pyridylmethyl)thio]glycosides (1a) using several activators is described. NBS-promoted glycosylation reaction utilizing either the α- or β-thiodideoxyglycoside proceeded smoothly at −78 °C to give the corresponding dideoxynucleoside in a β-selective manner, presumably through a common glycosyl donor.     

Moduli-induced gravitino problem

We investigate the cosmological moduli problem by studying a modulus decay in detail and find that the branching ratio of the gravitino production is generically of O(0.01-1), which causes another cosmological disaster. Consequently, the cosmological moduli problem cannot be solved simply by making the modulus mass heavier than 100 TeV. We also illustrate our results by explicitly calculating the branching ratio into the gravitinos in the mixed modulus-anomaly model.     

Synthesis of (-)-sordarin

The first total synthesis of (-)-sordarin (1) was accomplished exploiting the following key reactions: (i) Ag(I)-catalyzed oxidative radical cyclization of a cyclopropanol derivative leading to a bicyclo[5.3.0]decan-3-one skeleton; (ii) Pd(0)-catalyzed intramolecular allylation reaction resulting in the entire strained bicyclo[2.2.1]heptan-2-one framework of sordaricin (2); (iii) selective dihydroxylation of terminal alkenes by the combined use of OsO(4) and PhB(OH)(2); and (iv) beta(1,2-cis)-selective glycosidation via a 1,3-anchimeric assistance from a 4-methoxybenzoyl group.