Biosynthesis of yatein in Anthriscus sylvestris

Little is known about the biosynthesis of yatein, in spite of its importance as a typical heartwood lignan and a key biosynthetic intermediate of the antitumor lignan podophyllotoxin. The present study, based on individual administration of [13C]phenylalanine and deuterium labelled lignans and simultaneous administration of two distinct lignans labelled with deuterium atoms to Anthriscus sylvestris, established the two independent branch pathways from matairesinol, one to afford yatein via thujaplicatin, 5-methylthujaplicatin, and 4,5-dimethylthujaplicatin and the other to bursehernin via pluviatolide. The latter pathway did not lead to yatein, eliminating the presence of a metabolic grid from matairesinol to yatein.     

Vibrational spectra and crystal structure of ethyl methyl sulfide-mercury(II) chloride complex

The crystal structure of the ethyl methyl sulfide-mercury(II) chloride complex, CH₃SCH₂CH₃· HgCl₂, has been determined by X-ray diffraction. The conformation about the CS-CC axis of the complex is trans, which is different from the conformation of crystalline ethyl methyl sulfide. The Raman and IR spectra of the complex have been measured. Observed wavenumbers of the CH₂ rocking and C-C stretching vibrations of the complex are close to those of the trans form of ethyl methyl sulfide in the liquid state, but the wavenumber of the C-S stretching vibration shifts on formation of the S-Hg bond.     

Studies on pyrazines. Part 28 . Deoxydative acetoxylation of pyrazine N-oxides

Deoxydative acetoxylation of 3-methoxy-, 3-phenyl-, 3-methyl-, 3-chloro-, and 3-methoxycar-bonylpyrazine 1-oxides furnished predominantly 2-acetoxy-6-substituted pyrazines, some of which were more selectively prepared by addition of zinc bromide and triethylamine to the reaction. Regioselectivity of the acetoxylation is discussed based upon heat of formation by AMI and AMI-COSMO for all possible isomers of each set.     

Self-crosslinkable polymers. IV. Copolymerization of 1-ethenyl-4-(2,3-epoxy-1-propoxy)benzene with vinylpyridines

Soluble and self-crosslinkable linear copolymers with pendant epoxy and pyridyl groups were obtained from 1-ethenyl-4-(2,3-epoxy-1-propoxy)benzene (M₁) and vinylpyridines (M₂) by the action of α,α′-azobisisobutyronitrile. The monomer reactivity ratios were determined in tetrahydrofuran at 60°C (r₁, r₂, and vinylpyridine given): 0.467, 0.638, 4-vinylpyridine; 0.556, 1.25, 2-vinylpyridine; 0.639, 1.38, 5-ethyl-2-vinylpyridine. The Q and e values for 1-ethenyl-4-(2,3-epoxy-1-propoxy)-benzene were calculated as 1.3–1.6 and ?1.1–?1.3, respectively, with the reported Q–e values for these vinylpyridines. The intrinsic viscosities of the copolymers were found to be 0.15–0.30 in tetrahydrofuran at 30°C and to be dependent on the copolymer composition. The copolymers with these vinylpyridines were amorphous, had no clear melting points, and became insoluble crosslinked polymers under heating without further addition of any curing agents.     

Heat capacity and magnetic phase transition of two-dimensional metal-assembled complex (NEt<Subscript>4</Subscript>)[{Mn<Superscript>III</Superscript>(salen)}<Subscript>2</Subscript>Fe<Superscript>III</Superscript>(CN)<Subscript>6</Subscript>]

Summary Heat capacity measurements of the two-dimensional metal-assembled complex, (NEt₄)[{Mn^III(salen)}₂Fe^III(CN)₆] [Et=ethyl, salen= N,N’-ethylenebis(salicylideneaminato) dianion], were performed in the temperature range between 0.2 and 300 K by adiabatic calorimetry. A ferrimagnetic phase transition was observed at T_c1=7.51 K. Furthermore, another small magnetic phase transition appeared at T_c2=0.78 K. Above T_c1, a heat capacity tail arising from the short-range ordering of the spins characteristic of two-dimensional magnets was found. The magnetic enthalpy and entropy were evaluated to be ΔH=291 J mol^-1 and ΔS=27.4 J K^-1 mol^-1, respectively. The experimental magnetic entropy agrees roughly with ΔS=Rln(5·5·2) (=32.5 J K^-1 mol^-1; R being the gas constant), which is expected for the metal complex with two Mn(III) ions in high-spin state (spin quantum number S=2) and one Fe(III) ion in low-spin state (S=1/2). The heat capacity tail above T_c1 became small by grinding and pressing the crystal. This mechanochemical effect would be attributed to the increase of lattice defects and imperfections in the crystal lattice, leading not only to formation of the crystal with a different magnetic phase transition temperature but also to decrease of the magnetic heat capacity and thus the magnetic enthalpy and entropy.     

Interaction of toxic lectin ricin with epithelial cells of rat small intestine in vitro.

To clarify the mechanism of oral toxicity of ricin, the interaction of ricin with the epithelial cells isolated from rat small intestine was compared in vitro with those of other plant lectins by two different determinations, i.e., viability and cytotoxicity. After incubation of the cells for 1 h at 37 degrees C with ricin, B-chain, castor bean hemagglutinin (CBH), soybean agglutinin (SBA), wheat germ agglutinin (WGA), concanavalin A (Con A), and peanut agglutinin (PNA), respectively, followed by staining with trypan blue, ricin and ricin B-chain as well as CBH and SBA were found to have effectively reduced the number of viable cells. On the contrary, only ricin inhibited protein synthesis in the cells and the effect was blocked by D-galactose. Additional experiments employing [125I]-labeled ricin strongly suggested that ricin was first bound via its B-chain to the galactosyl residues on the cell surface followed by internalization into cells as the whole 62 kDa molecule. These results infer first that ricin, as well as other lectins mentioned above, was able to reduce viability of the epithelial cells of rat small intestine by direct binding to the cell surface. The second effect, specific to ricin, was the inhibition of cellular protein synthesis.     

Effects of (+)-, (-)- and (+/-)-indenestrols A and B on microtubule polymerization.

Indenestrol A (IA) is a metabolite of diethylstilbestrol (DES), and indenestrol B (IB) is an analog of IA. IA was simply obtained from E,E-dienestrol in the presence of dilute sulfuric acid, and a mixture of IA and IB was formed by thermal cyclization of E,E-dienestrol. In order to elucidate the effects of optically active IA and IB on microtubule assembly, the IA and IB enantiomers were separated to greater than 99% purity by high-pressure liquid chromatography using a chiral column. The di(4-bromobenzoate) of (-)-IB was analyzed by X-ray crystallography and its absolute structure was determined as C(3)-S. The (+)-, (-)-, and (+/-)-indenestrols A and B were shown to be inhibitors of microtubule assembly in vitro using microtubule proteins from porcine brain. (+/-)-IB is more active than (+/-)-IA, and the order of inhibitory activity of the enantiomers on microtubule assembly was (+)-IB greater than (+)-IA greater than (-)-IA greater than (-)-IB.     

Assessment of endoglucanase activity by analyzing the degree of cellulose polymerization and high-throughput analysis by near-infrared spectroscopy

We developed a novel and practical assessment technique for endoglucanase (EG) activity by measuring the degree of polymerization (DP) of cellulose from Eucalyptus globulus. This evaluation method demonstrated that EG II from Trichoderma reesei had higher endoglucanase activity than EG I, which has not been detected in conventional experiments using carboxymethyl cellulose as a model substrate. In addition, a high-throughput protocol for DP measurement was developed by using near-infrared spectroscopy combined with a multivariate analysis. Interpreting the regression coefficient, a reciprocal correlation was observed between the relative crystallinity of the cellulosic residue after enzymatic hydrolysis and the DP.     

Metamagnetic quantum criticality revealed by 17O-NMR in the itinerant metamagnet Sr3Ru2O7

We have investigated the spin dynamics using 17O-NMR in the bilayered perovskite Sr3Ru2O7, which sits close to a metamagnetic quantum critical point. The nuclear spin-lattice relaxation rate divided by temperature 1/T1T is enhanced on approaching the metamagnetic critical field of approximately 7.9 T, and at the critical field 1/T1T continues to increase and does not show Fermi-liquid behavior down to 0.3 K. The temperature dependence of T1T in this region suggests the critical temperature Theta to be approximately 0 K, which is strong evidence that the spin dynamics possesses a quantum critical character. Comparison between uniform susceptibility and 1/T1T reveals that antiferromagnetic fluctuations instead of two-dimensional ferromagnetic fluctuations dominate the spin fluctuation spectrum at the critical field, which is unexpected for itinerant metamagnetism.     

Reaction of grayanotoxin-II with thallium (III) nitrate

Reaction of grayanotoxin-II (1) with thallium nitrate gave 3(S), 20-epoxy-6 (S), 14 (R), 16 (R)-trihydroxy-5-oxo-5, 10-seco-ent-kaur-1 (10) -ene (2). The structure of 2 was elucidated by the X-ray diffraction analysis of its reduction product (3).