Mn(III)-based reaction of alkenes with quinolinones. Formation of peroxyquinolinones and quinoline-related derivatives

The reactions of 1,1-disubstituted alkenes with 4-hydroxyquinolin-2(1H)-ones under both Mn(III)-catalyzed aerobic oxidation conditions at room temperature and Mn(III)-mediated oxidation conditions at reflux temperature are described. The Mn(III)-catalyzed aerobic oxidation afforded bis(hydroperoxyethyl)quinolinones and azatrioxa[4.4.3]propellanes, while the oxidation with Mn(OAc)₃·2H₂O produced furo[3,2-c]quinolin-4-one analogues. The existence of a substituent at the 3-position of the 4-hydroxyquinolin-2(1H)-ones prevented a double reaction with the alkenes, and (endoperoxy)quinolinones and/or (hydroperoxyethyl)quinolinones were obtained under the Mn(III)-catalyzed aerobic conditions, while furo[3,2-c]quinolinone hemiacetals and vinylquinolinones were selectively produced under the Mn(III)-mediated oxidation conditions depending on the reaction temperature and times. Cyclic assembly of quinolinone-related 1,3-dicarbonyl compounds such as dihydropyridinones, pyranones, and dimedone derivatives was also examined under elevated temperature conditions.     

Synthesis and characterisation of p-diethylaminomethylthiacalix[4]arene for selective recovery of platinum from automotive catalyst residue

The ability of chloroform solutions of p-diethylaminomethylthiacalix[4]arene 1 to extract platinum from HCl media was tested. As an ion-pair extractant, compound 1 had the highest platinum extraction ability among all the thiacalix[n]arene derivatives tested in this study. Compound 1 was a highly specific extractant for Pt(IV) ions from single-metal solutions and platinum-group metal solutions from automotive catalyst residue. Various conditions such as contact time, pH, concentration of 1, effect of chloride ions, effect of acidity and Pt(IV) concentration were studied. The distribution ratio of platinum ions (D) was calculated. The platinum complex stoichiometry ratio was obtained using slope analysis. The 1–Pt(IV) complex was characterised using X-ray photoelectron spectroscopy, FT-IR and ¹H NMR. Finally, the Pt(IV) extraction percentage of compound 1 was compared with that of previously reported thiacalix[n]arene-based extractants.     

Diastereo‐ and Enantioselective anti‐Selective Hydrogenation of α‐Amino‐β‐keto Ester Hydrochlorides and Related Compounds Using Transition‐Metal–Chiral‐Bisphosphine Catalysts

This review describes our recent works on the diastereo‐ and enantioselective synthesis of anti‐β‐hydroxy‐α‐amino acid esters using transition‐metal–chiral‐bisphosphine catalysts. A variety of transition metals, namely ruthenium (Ru), rhodium (Rh),iridium (Ir), and nickel (Ni), in combination with chiral bisphosphines, worked well as catalysts for the direct anti‐selective asymmetric hydrogenation of α‐amino‐β‐keto ester hydrochlorides, yielding anti‐β‐hydroxy‐α‐amino acid esters via dynamic kinetic resolution (DKR) in excellent yields and diastereo‐ and enantioselectivities. The Ru‐catalyzed asymmetric hydrogenation of α‐amino‐β‐ketoesters via DKR is the first example of generating anti‐β‐hydroxy‐α‐amino acids. Complexes of iridium and axially chiral bisphosphines catalyze an efficient asymmetric hydrogenation of α‐amino‐β‐keto ester hydrochlorides via dynamic kinetic resolution. A homogeneous Ni–chiral‐bisphosphine complex also catalyzes an efficient asymmetric hydrogenation of α‐amino‐β‐keto ester hydrochlorides in an anti‐selective manner. As a related process, the asymmetric hydrogenation of the configurationally stable substituted α‐aminoketones using a Ni catalyst via DKR is also described.     

Metabolomics of lung cancer: Analytical platforms and their applications

Lung cancer is the leading type of cancer worldwide in terms of the number of new cases and is responsible for the largest number of deaths due to poor prognosis and difficult early detection. Due to its ability to detect numerous small molecular metabolites simultaneously, metabolomics has been widely used for the assessment of global metabolic changes in a living organism to discover candidate biomarkers for cancer diagnosis, investigate the development of cancer, and provide insights into the underlying pathophysiology. This review will mainly describe recent developments in lung cancer metabolomics in terms of early‐stage detection, biomarker discovery and mechanism exploration by using nuclear magnetic resonance, liquid chromatography–mass spectrometry, gas chromatography–mass spectrometry, and capillary electrophoresis–mass spectrometry in the last 10 years. The sample collection and metabolite extraction methods are also summarized.     

New measurements and reanalysis of 14N elastic scattering on 10B target

The angular distributions of elastic scattering of ¹⁴N ions on ¹⁰B targets have been measured at incident beam energies of 21.0 and 24.5 MeV. Angular distributions at higher energies 38–94.0 MeV (previously measured) were also included in the analysis. All data were analyzed within the framework of the optical model and the distorted waves Born approximation method. The observed rise in cross sections at large angles was interpreted as a possible contribution of the α-cluster exchange mechanism. Spectroscopic amplitudes SA₂ and SA₄ for the configuration ¹⁴N→ ¹⁰B +α were extracted. Their average values are 0.58±0.10 and 0.81±0.12 for SA₂ and SA₄, respectively, suggesting that the exchange mechanism is a major component of the elastic scattering for this system. The energy dependence of the depths for the real and imaginary potentials was found.     

Antimicrobial and Antioxidant Properties of Total Polyphenols of Anchusa italica Retz

Anchusa italica Retz has been used for a long time in phytotherapy. The aim of the present study was to determine the antioxidant and antibacterial activities of extracts from the leaves and roots of Anchusa italica Retz. We first determined the content of phenolic compounds and flavonoids using Folin–Ciocalteu reagents and aluminum chloride (AlCl₃). The antioxidant activity was determined using three methods: reducing power (FRAP), 2.2-diphenyl-1-picrylhydrazyl (DPPH), total antioxidant capacity (TAC). The antimicrobial activity was investigated against four strains of Escherichia coli, two strains of Klebsiella pneumoniae and coagulase-negative Staphylococcus, and one fungal strain of Candida albicans. The results showed that the root extract was rich in polyphenols (43.29 mg GAE/g extract), while the leave extract was rich in flavonoids (28.88 mg QE/g extract). The FRAP assay showed a strong iron reduction capacity for the root extract (IC₅₀ of 0.11 µg/mL) in comparison to ascorbic acid (IC₅₀ of 0.121 µg/mL). The DPPH test determined an IC₅₀ of 0.11 µg/mL for the root extract and an IC₅₀ of 0.14 µg/mL for the leaf extract. These values are low compared to those for ascorbic acid (IC₅₀ of 0.16 µg/mL) and BHT (IC₅₀ 0.20 µg/mL). The TAC values of the leaf and root extracts were 0.51 and 0.98 mg AAE/g extract, respectively. In vitro, the extract showed inhibitory activity against all strains studied, with diameters of zones of inhibition in the range of 11.00–16.00 mm for the root extract and 11.67–14.33 mm for the leaf extract. The minimum inhibitory concentration was recorded for the leaf extract against E. coli (ATB:57), corresponding to 5 mg/mL. Overall, this research indicates that the extracts of Anchusa italica Retz roots and leaves exert significant antioxidant and antibacterial activities, probably because of the high content of flavonoids and polyphenols.     

Formation of polymeric micelles with amino surfaces from amphiphilic AB‐type diblock copolymers composed of poly(glycolic acid lysine) segments and polylactide segments

Amphiphilic AB‐type diblock copolymers composed of hydrophobic poly(L ‐lactide) (PLA) segments and hydrophilic poly(glycolic acid lysine) [poly(Glc‐Lys)] segments with amino side‐chain groups self‐associated to form PLA‐based polymeric micelles with amino surfaces in an aqueous solution. The average diameter of the loose core–shell polymeric micelles for poly(Glc‐Lys) [number‐average molecular weight (M_n) = 1240]‐b‐PLA (M_n = 7000) obtained by a dimethyl sulfoxide/water dialysis method was estimated to be about 50 nm in water by dynamic light scattering measurements. The size and shape of the obtained polymeric micelles were further observed with transmission electron microscopy and atomic force microscopy. To investigate the possibility of applying the obtained PLA‐based polymeric micelles as bioabsorbable vehicles for hydrophobic drugs, we tested the entrapment of drugs in poly(Glc‐Lys) (M_n = 1240)‐b‐PLA (M_n = 7000) micelles and their release with doxorubicin as a hydrophobic drug. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1426–1432, 2002     

Observation of the fast potential change at L-H transition by a heavy-ion-beam probe on JFT-2M

The fast potential change near the separatrix is measured directly at the L-H transition by a heavy-ion-beam probe. The potential changes with two different time scales at the L-H transition triggered by a sawtooth crash: it drops at first with the time scale of 10--100 mus just after the arrival of the heat pulse due to the sawtooth crash. Then, it decreases again at a few 100 mus after the first drop at a time scale of about 200 mus.     

Achievement of a 920-MHz high resolution NMR

We have developed a 920-MHz NMR system and performed the proton NMR measurement of H(2)O and ethylbenzene using the superconducting magnet operating at 21.6 T (920 MHz for proton), which is the highest field produced by a superconducting NMR magnet in the persistent mode. From the NMR measurements, it is verified that both homogeneity and stability of the magnet have a specification sufficient for a high resolution NMR.