Determination of psilocybin in hallucinogenic mushrooms by reversed-phase liquid chromatography with fluorescence detection

The determination of psilocybin was carried out by reversed-phase liquid chromatography (HPLC) with fluorescence (FL) detection. Psilocybin was labeled with 5-dimethylaminonaphthalene-1-[N-(2-aminoethyl)]sulfonamide (DNS-ED) at 60 °C for 4 h in the presence of 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC) as the activation reagent. The resulting derivative was separated on a Mightysil RP-18 GP column (150 mm × 4.6 mm, i.d. 3 μm) with the mixture of 50 mM ammonium acetate (AcONH₄) and CH₃CN, and detected at 539 nm (excitation at 321 nm). The structure of the derivative was identified by HPLC-ESI-MS. A good linear relation of the calibration curve of psilocybin was observed under the proposed conditions for labeling, separation and detection. The quantification limit was 4.4 ng in 1 mg dried mushroom. The proposed procedure was successfully used for the determination of psilocybin in real samples. The contents of psilocybin in six magic mushrooms by the proposed HPLC-FL method were less than 20.0 ng in 1 mg dried samples.     

Phase diagrams of lyotropic cholesteric fluids

Experimental investigations of lyotropic cholesterics fluids are presented which show that changes in the shape anisotropy and chirality of the micellar population determine the topology of the temperature-concentration phase diagrams. For given amounts of the substances which induce the chirality and modify the shape anisotropy of the micelles, two distinct biaxial cholesteric phases are disclosed in the phase diagrams. This is interpreted in the framework of the catastrophe theory of phase transitions.     

Gastric acidity-dependent bioavailability of commercial sustained release preparations of indomethacin, evaluated by gastric acidity-controlled beagle dogs

The relationship between gastric acidity and the bioavailability of two kinds of sustained-release indomethacin (IM) formulations was investigated in gastric acidity-controlled beagle dogs, and compared with that of rapid-release IM formulations. All test dosage forms were more rapidly dissolved in simulated intestinal fluid than in simulated gastric fluid. Gastric acidity did not affect the bioavailability of IM from the rapid-release formulation. However, the bioavailability of IM from the two kinds of sustained-release formulations were markedly influenced by gastric acidity. The rates of IM bioavailability from both of the sustained-release formulations were faster under low acidity conditions than under high acidity conditions (p less than 0.01). In addition, Tmax and mean residence time (MRT) were approximately the same for the rapid-release and sustained-release formulations under low acidity conditions. These results suggest that the IM sustained-release formulations showed a rapid-release profile under low acidity conditions.     

Unique sugar metabolism and novel enzymes of hyperthermophilic archaea

Hyperthermophiles are a group of microorganisms that have their optimum growth temperature above 80 degrees C. More than 60 species of the hyperthermophiles have been isolated from marine and continental volcanic environments. Most hyperthermophiles belong to Archaea, the third domain of life, and are considered to be the most ancient of all extant life forms. Recent studies have revealed the presence of unusual sugar metabolic processes in hyperthermophilic archaea, for example, a modified Embden-Meyerhof pathway, that has so far not been observed in bacteria and eucarya. Several novel enzymes, such as ADP-dependent glucokinase, ADP-dependent phosphofructokinase, glyceraldehyde-3-phosphate ferredoxin oxidoreductase, phosphoenolpyruvate synthase, pyruvate : ferredoxin oxidoreductase, and ADP-forming acetyl-CoA synthetase, have been found to be involved in a modified Embden-Meyerhof pathway of the hyperthermophilic archaeon Pyrococcus furiosus. In addition, a unique mode of ATP regeneration has been postulated to exist in the pathway of P. furiosus. The metabolic design observed in this microorganism might reflect the situation at an early stage of evolution.     

A new methodology for the oxidation of sulfides with Fe(III) catalysts

A variety of sulfides were converted to the corresponding sulfoxide derivatives with 70% t‐BuOOH (water) as the oxidant in the presence of catalytic quantity of Fe₂(SO₄)₃. The method described has a wide range of applications, involves simple work‐up, exhibits chemoselectivity/enantioselectivity and proceeds under mild reaction conditions. The resulting products are obtained in good yield within a reasonable time. Copyright © 2012 John Wiley & Sons, Ltd.     

Creep-rupture lifetime simulation of unidirectional metal matrix composites with and without time-dependent fiber breakage

A numerical simulation for predicting the axial creep-rupture lifetime of continuous fiber-reinforced metal matrix composites is proposed, based on the finite element method. The simulation model is composed of line elements representing the fibers and four-node isoparametric plane elements representing the matrix. While the fibers behave as an elastic body at all times, the matrix behaves as an elasto-plastic body at the loading process and an elasto-plastic creep body at the creep process. It is further assumed in the simulation that the fibers are fractured not only in stress criterion but time-dependently with random nature. Simulation results were compared with the creep-rupture lifetime data of a boron-aluminum composite with 10% fiber volume fraction experimentally obtained. The simulated creep-rupture lifetimes agreed well with the averages of the experimental data. The proposed simulation is further carried out to predict a possibility of creep-rupture for the composite without time-dependent fiber breakage. It is finally concluded that the creep-rupture of a boron-aluminum composite is closely related with the shear stress relaxation occurring in the matrix as well as time-dependent fiber breakage.     

On the L p discrepancy of two-dimensional folded Hammersley point sets

We give an explicit construction of two-dimensional point sets whose L _p discrepancy is of best possible order for all \({1 \le p \le \infty}\) . It is provided by folding Hammersley point sets in base b by means of the b-adic baker’s transformation which has been introduced by Hickernell (Monte Carlo and quasi-Monte Carlo methods. Springer, Berlin, 274–289, 2002) for b =  2 and Goda, Suzuki, and Yoshiki (The b-adic baker’s transformation for quasi-Monte Carlo integration using digital nets. arXiv:1312.5850 [math:NA], 2013) for arbitrary \({b \in \mathbb{N}}\) , \({b \ge 2}\) . We prove that both the minimum Niederreiter–Rosenbloom–Tsfasman weight and the minimum Dick weight of folded Hammersley point sets are large enough to achieve the best possible order of L _p discrepancy for all \({1 \le p \le \infty}\) .     

Identification of a novel cannabimimetic phenylacetylindole, cannabipiperidiethanone, as a designer drug in a herbal product and its affinity for cannabinoid CB₁ and CB₂ receptors

A new cannabimimetic phenylacetylindole (cannabipiperidiethanone, 1) has been found as an adulterant in a herbal product which contains two other known synthetic cannabinoids, JWH-122 and JWH-081, and which is distributed illegally in Japan. The identification was based on analyses using GC-MS, LC-MS, high-resolution MS and NMR. Accurate mass spectrum measurement showed the protonated molecular ion peak of 1 at m/z 377.2233 [M+H]? and the molecular formula of 1 was C??H??N?O?. Both mass and NMR spectrometric data revealed that 1 was 2-(2-methoxyphenyl)-1-{1-[(1-methylpiperidin-2-yl)methyl]-1H-indol-3-yl}ethanone. Compound 1 has a mixed structure of known cannabimimetic compounds: JWH-250 and AM-2233. Namely, the moiety of phenylacetyl indole and N-methylpiperidin-2-yl-methyl correspond to the structure of JWH-250 and AM-2233, respectively. However, no synthetic, chemical or biological information about 1 has been reported. A binding assay of compound 1 to cannabinoid receptors revealed that 1 has affinity for the CB? and CB? (IC??=591, 968 nM, respectively) receptors, and shows 2.3- and 9.4-fold lower affinities than those of JWH-250. This is the first report to identify cannabimimetic compound (1) as a designer drug and to show its binding affinity to cannabinoid receptors.     

NMR-based characterization of a novel yellow chlorophyll catabolite, Ed-YCC,isolated from Egeria densa

A novel yellow chlorophyll catabolite, Ed-YCC, was isolated from leaves detached from Egeria densa shoots, in which chlorophyll degradation and anthocyanin synthesis were induced in 0.1 M fructose solution under light illumination as a plant senescence process, a model of autumnal leaf coloration. Structure elucidation was accomplished by various NMR techniques including 2D-INADEQUATE.