Asymmetric total syntheses of (+)-mycoepoxydiene and related natural product (-)-1893A: application of one-pot ring-opening/cross/ring-closing metathesis to construct their 9-oxabicyclo[4.2.1]nona-2,4-diene skeleton

The total syntheses of (+)-mycoepoxydiene and (-)-1893A have been completed. The present synthetic strategy features the use of one-pot ring-opening/cross metathesis (ROM/CM) followed by a ring-closing metathesis (RCM) reaction, allowing for the concise construction of the 9-oxabicyclo[4.2.1]nona-2,4-diene framework from a 7-oxabicyclo[2.2.1]hept-2-ene derivative and 1,3-butadiene. The sequential metathesis product was converted into (+)-mycoepoxydiene through the oxidative rearrangement of a furfuryl alcohol to a pyranone, thereby establishing its absolute stereochemistry. From the common intermediate, a structurally related natural product (-)-1893A was also synthesized via the vinylogous aldol reaction.     

Synthesis of poly(2,5-dimethylphenylene sulfide) through oxidative polymerization of sulfur chloride with p-xylene

Poly(2,5-dimethylphenylene sulfide) was prepared by oxidative polymerization of sulfur chloride with p-xylene using 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) as an oxidizing agent. The reaction proceeded efficiently under atmospheric pressure and at room temperature. The polymer formed had a high melting temperature and linear structure which was confirmed by spectroscopies. The effects of reaction time, solvent, temperature and oxidizing agent on polymerization are also discussed.     

Synthesis and properties of rhenium tricarbonyl complex bearing N-fused tetraphenylporphyrin ligand

An N-fused porphyrin rhenium complex was synthesized by the thermal reaction of an N-confused porphyrin with Re2(CO)10 and its structure was determined by X-ray crystallographic analysis.     

Determination of daidzein and genistein in soybean foods by automated on-line in-tube solid-phase microextraction coupled to high-performance liquid chromatography

An automated on-line method for the determination of the isoflavones, daidzein and genistein, was developed using in-tube solid-phase microextraction coupled to high-performance liquid chromatography (in-tube SPME-HPLC). In-tube SPME is a new extraction technique for organic compounds in aqueous samples, in which analytes are extracted from the sample directly into an open tubular capillary by repeated draw/eject cycles of sample solution. Daidzein, genistein and their glucosides tested in this study were clearly separated within 8 min by HPLC using an XDB-C8 column with diode array detection. In order to optimize the extraction of these compounds, several in-tube SPME parameters were examined. The glucosides daidzin and genistin were analyzed as aglycones after hydrolysis because the glucosides were not concentrated by in-tube SPME. The optimum extraction conditions for daidzein and genistein were obtained with 20 draw/eject cycles of 40 microl of sample using a Supel-Q porous layer open tubular capillary column. The extracted compounds were easily desorbed from the capillary by mobile phase flow, and carryover was not observed. Using the in-tube SPME-HPLC method, the calibration curves of these compounds were linear in the range 5-200 ng/ml, with a correlation coefficient above 0.9999 (n = 18), and the detection limits (S/N = 3) were 0.4-0.5 ng/ml. This method was successfully applied to the analysis of soybean foods without interference peaks. The recoveries of aglycones and glucosides spiked into food samples were above 97%.     

The dependence of cyclopolymerizability of acrylic and methacrylic anhydrides on various conditions: New interpretation of temperature dependency of cyclization constant in radical cyclopolymerization of nonconjugated dienes

The cyclization constant K_c in the radical cyclopolymerization of acrylic and methacrylic anhydrides was evaluated in detail under various conditions. No linear relationship between in K_c and 1/T was observed; cyclization was acceleratively enhanced at elevated temperatures. The K_c values also increased with decreased monomer concentration and increased solvent polarity. These increasing dependencies of K_c are ascribed to the increased significance of depropagation, demonstrating a new interpretation of the temperature dependence of the cyclization constant in the radical cyclopolymerization of nonconjugated dienes.     

Effects of poly(ethylene glycol) (PEG) concentration on the permeability of PEG-grafted liposomes

Poly(ethylene glycol)-grafted liposomes (PEG-liposomes) were prepared from dipalmitoylphosphatidylcholine (DPPC) with various amounts of distearoyl-N-monomethoxy poly(ethylene glycol)-succinyl-phosphatidylethanolamines (DSPE-PEG) with PEG molecular weights of 1000, 2000, 3000 and 5000. The effects of DSPE-PEG concentration on the permeability of PEG-liposomes were investigated using carboxyfluorescein (CF). In the gel state, the CF leakage from PEG-liposomes was decreased with increasing mole fractions of DSPE-PEG for all PEG molecular weights. In the liquid-crystalline state, the CF leakage from PEG-liposomes containing DSPE-PEG1000 gradually increased with increasing mole fractions of DSPE-PEG, while that of PEG-liposomes whose molecular weight in PEG units was above 2000 rapidly decreased by the addition of DSPE-PEG. Furthermore, no effect of PEG molecular weight on CF leakage was observed. The relationship between the fluorescence polarization of 1,6-diphenyl-1,3,5-hexatriene (DPH) (or 1-(4-trimethylammoniumphenyl)-6-phenyl-1,3,5-hexatriene (TMA-DPH)) and the mole fraction of DSPE-PEG for PEG-liposomes was also investigated. No significant changes in fluorescence polarization of DPH for liposomal bilayer membranes was observed in the gel and liquid-crystalline states due to the addition of DSPE-PEG, while that of TMA-DPH was decreased compared with that of liposomes without DSPE-PEG in both states.     

Effect of HF addition on the microwave-assisted acid-digestion for the determination of metals in coal by inductively coupled plasma-atomic emission spectrometry

The microwave-assisted acid-digestion for the determination of metals in coal by ICP-AES was investigated, especially focusing on the necessity of adding HF. By testing five certified reference materials, BCR-180, BCR-040, NIST-1632b, NIST-1632c, and SARM-20, it was found that the two-stage digestion without HF (HNO₃ + H₂O₂ was used) was very effective for the pretreatment of ICP-AES measurement. Both major metals (Al, Ca, Fe, and Mg) and minor or trace metals (Co, Cr, Cu, Mn, Ni, Pb, and Zn) in coal gave good recoveries for their certified or reference values. The possibility of ‘HF-memory effect’ was cancelled by the use of a set of vessels which had been never contacted with HF. Twenty-four Japanese standard coals (SS coals) were analyzed by the present method, and the concentrations of major metals measured by the present method provided very high accordance with those from the authentic JIS (Japanese Industrial Standard) method.     

A New Approach to the Construction of BEDT-TTF Derivatives Condensed with Heterocycles via BF3-promoted Reactions of Organotin Thiolates

The synthesis of BEDT-TTF derivatives fused with heterocycles (3–7) has been accomplished via the BF₃-promoted reaction of organotin thiolates (8 and 9) with electrophiles (10 and 11). Electrical conductivities of radical cation salts derived from some of them were also investigated.     

Two-dimensional network formation of cardiac myocytes in agar microculture chip with 1480 nm infrared laser photo-thermal etching

We have developed a new method that enables agar microstructures to be used to cultivate cells and that allows cell network patterns to be controlled. The method makes use of non-contact three-dimensional photo-thermal etching with a 1480 nm infrared focused laser beam, which is strongly absorbed by water and agar gel, to form the shapes of agar microstructures. It allows microstructures to be easily formed in an agar layer within a few minutes, with cell-culture holes formed by the spot heating of a 100 mW laser and tunnels by the tracing of a 100 microm s(-1), 40 mW laser. We cultivated rat cardiac myocytes in adjacent microstructures and observed synchronized beating in them 90 min after they had made physical contact. Our results indicate that the system can make and use microstructures for cell-network cultivation in a minimal amount of time without any expensive microfabrication facilities or complicated procedures.     

Structure-specificity relationship of cardiac glycosides as a substrate for glucohydrolase II

Cardenolide glucohydrolase II (CGH II) is a cardenolide-specific glucohydrolase obtained from Digitalis lanata leaves. We investigated the structure-specificity relationship of several cardenolide disaccharides as a substrate for CGH II. Conformation analysis of the substrates was performed using molecular mechanics calculations. The sugar chain conformation of two inert glycosides was significantly different from that of the other glycosides. The other two glycosides, which were weak substrates of CGH II, were suggested to have an intramolecular hydrogen bond between the sugar groups. It was deduced that this hydrogen bond restricts the conformational change of the sugar chain and prevents the glycosides from enzymatic recognition.