Asymmetric synthesis of abietane diterpenoids via B-alkyl Suzuki-Miyaura coupling. Formal total asymmetric synthesis of 12-deoxyroyleanone and cryptoquinone

A convergent synthetic strategy for abietane diterpenoids via B-alkyl Suzuki-Miyaura coupling and Lewis acid-mediated cyclization reactions is established. Asymmetric total synthesis of 12-deoxyroyleanone, an antileishmanial diterpene, is described.     

Synthesis and absolute configuration of cordiaquinone K, antifungal and larvicidal meroterpenoid isolated from the Panamanian plant, Cordia curassavica

Total synthesis of cordiaquinone K, a new antifungal and larvicidal meroterpenoid, is reported. The absolute configuration of cordiaquinone K was confirmed by the synthesis.     

Structures and conformations of metabolites of antitumor cyclic hexapeptides, RA-VII and RA-X.

Metabolites of antitumor cyclic hexapeptides, RA-VII and -X which were isolated from Rubia cordifolia were studied by hepatic microsomal biotransformation in rats and in bile juice of rabbits to which these drugs were administered intravascularly. Their structures and conformations were elucidated by two-dimensional nuclear magnetic resonance techniques, temperature effect on NH protons and nuclear Overhauser effect experiments. Specific N-demethylation of Tyr-3, O-demethylation and hydroxylation at aromatic rings of Tyr-3 and -5 were observed. Compared with metabolites of RA-VII, most of RA-X was excreted unchanged in the bile juice. Relationship among their structures, conformations and antitumor activities is also discussed.     

A new method for the synthesis of some 9-β-D-arabinofuranosylpurines by a combination of chemical and enzymatic reactions

An enzymatic transarabinosylation between 2-chlorohypoxanthine and 1-β-$\text{D}$-arabinofuranosyluracil gave 9-β-$\text{D}$-arabinofuranosyl-2-chlorohypoxanthine which was chemically converted to 9-β-$\text{D}$-arabinofuranosylguanine and its derivatives.     

Asymmetric synthesis of the hydronaphthalene moieties of mevinic acids

The hydronaphthalene moieties of mevinic acids are synthesized enantioselectively by using the asymmetric intramolecular Diels-Alder reaction catalyzed by a chiral titanium reagent.     

Improving the properties of the proton exchange membranes by introducing α-methylstyrene in the pre-irradiation induced graft polymerization

New proton exchange membranes (PEMs) were prepared by pre-irradiation induced grafting of α-methylstyrene (AMS)/styrene (STY)/divinylbenzene (DVB) into the crosslinked polytetrafluoroethylene (RX-PTFE) films and successively sulfonated. The new PEMs showed the improved glass transition temperature and chemical stability as compared with the PEMs prepared by pre-irradiation induced grafting of STY/DVB. The balance of the cost, grafting kinetic, thermal properties and the properties of the resulted proton exchange membrane is the key point of this work.     

Donor–acceptor–acceptor-type near-infrared fluorophores that contain dithienophosphole oxide and boryl groups: effect of the boryl group on the nonradiative decay

The use of donor–π–acceptor (D–π–A) skeletons is an effective strategy for the design of fluorophores with red-shifted emission. In particular, the use of amino and boryl moieties as the electron-donating and -accepting groups, respectively, can produce dyes that exhibit high fluorescence and solvatochromism. Herein, we introduce a dithienophosphole P-oxide scaffold as an acceptor–spacer to produce a boryl- and amino-substituted donor–acceptor–acceptor (D–A–A) π-system. The thus obtained fluorophores exhibit emission in the near-infrared (NIR) region, while maintaining high fluorescence quantum yields even in polar solvents (e.g. λ_em = 704 nm and Φ_F = 0.69 in CH₃CN). A comparison of these compounds with their formyl- or cyano-substituted counterparts demonstrated the importance of the boryl group for generating intense emission. The differences among these electron-accepting substituents were examined in detail using theoretical calculations, which revealed the crucial role of the boryl group in lowering the nonradiative decay rate constant by decreasing the non-adiabatic coupling in the internal conversion process. The D–A–A framework was further fine-tuned to improve the photostability. One of these D–A–A dyes was successfully used in bioimaging to visualize the blood vessels of Japanese medaka larvae and mouse brain.

Combination of electron-accepting diarylboryl terminal groups and dithienophosphole oxide spacers with electron-donating triarylamine moieties produces donor–acceptor–acceptor type π-systems, which exhibit emissions in the near-infrared region.     

Uneven distribution of ventilation—perfusion ratios in lungs estimated by a modified Newton method

The uneven distribution of ventilation—perfusion ratios ( ) in diseased lungs is the major cause of arterial hypoxemia. Farhi and Yokoyama (1967) and Yokoyama and Farhi (1967) were the first who used physiologically inert gases as indicator gases to assess the uneven distribution of Wagner and his coworkers in San Diego (1977b) extended the method and elaborated the multiple inert gas elimination technique in which blood flows in 50 compartments with different were estimated based on data for 6 indicator gases. They analyzed the indicator gas data through an enforced smoothing technique with the ridge regression. To get smooth distributions, they introduced a weighting function for compartments and an additional treatment for the non-negativity of the blood flow. The weighting function was empirically obtained. We analyzed the data without putting any weights on compartments nor any additional treatment for non-negativity of blood flow. The analytical method in the present study was a modified Newton method, which is one of the enforced smoothing method. Our method was capable of recovering all distribution patterns that were found through the method reported by Wagner et al. (1977b).     

A Novel Synthesis of α-Tellanyl α,β-Unsaturated Aldehydes Using α-Tellanyl β-Alkoxyalkenyl Lithiums

Abstract

β-Ethoxy-α-phenyltellanylvinyl lithiums were successfully generated in situ from phenyltellanylacetaldehyde diethyl acetal with lithium 2,2,6,6-tetrame-thylpiperidide (LTMP) and underwent methylation or nucleophilic addition with aldehydes and ketones. The successive dehydration of the allylic alcohols with trimethylsilyl trifluoromethanesulfonate (TMSOTf) gave α-phenyltellanyl α,β-unsaturated aldehydes, which transformed to some useful compounds.     

Ion-Selective Electrodes Based on Bilayer Film Coating

The electrode characteristics of ion-selective electrodes (ISEs) for K⁺, Na⁺, NH₄ ⁺, and Ca²⁺ based on bilayer film coatings, where the inner layer films are electroactive electropolymerized ones and the outer layer films are composed of conventional ion-sensitive materials, have been examined. These ISEs of the coated-wire electrode type have no conventional internal reference solution and reference electrode, but the inner films may be considered to function as the “internal standard solution.” The ion selectivity coefficients and the activity range showing Nernstian response were almost comparable to those of conventional liquid-membrane electrodes. The bilayer-coated ISEs showed insensitivity to O₂ and CO₂, long-term stability, and little drift. It was also found that the electrode performance is practically unchanged after sterilization in an autoclave. The results demonstrate that the bilayer-coated ISEs examined are promising for the determination of K⁺, Na⁺, NH₄ ⁺, or Ca²⁺ activity in biological and environmental systems.