Field desorption mass spectrometry of natural products—I: Steroid- and triterpene saponins

Field desorption mass spectra of underivatized oligoglycosides of spirostanol and its congeners and of hederagenin revealed the molecular weight and structural information. The basic predominance of the formation of stable ions of highly polar natural products (with 5–17 free OH functions) is clearly demonstrated. After the extraction and purification procedure from plant material the samples contained inorganic salts in concentrations between 0.01 and 0.1%. These salt impurities, mostly alkali halides, strongly promoted the attachment of alkali cations to the intact molecules and their fragments. The ions produced gave analytical information not only for the confirmation of the molecular weight but also for the identity of the aglycone and, to some extent, for the sequence of the sugars in the oligoglycosides. All spectra were recorded on photoplates at a resolution of better than 15000 and enabled the evaluation of the elemental composition of the ions generated. The drawbacks and merits of integrating ion recording using the photoplate for FD investigations of highly polar substances are discussed.     

Kink dynamics in one-dimensional nonlinear systems

A certain class of nonlinear evolution equations of one space dimension which permits kink type solutions and includes one-dimensional time-dependent Ginzburg-Landau (TDGL) equations and certain nonlinear wave equations is studied in some strong coupling approximation where the problem can be reduced to the study of kink dynamics. A detailed study is presented for the case of TDGL equation with possible applications to the late stage kinetics of order-disorer phase transitions and spinodal decompositions. A special case of kink dynamics of nonlinear wave equations is found to reduce to the Toda lattice dynamics. A new conservation law for dissipative systems is found which corresponds to the momentum conservation law for wave equations.     

Photodissociation of molecular beams of halogenated hydrocarbons at 193 nm

Molecular beams of halogenated hydrocarbons containing chlorine and bromine atoms were photodissociated using an excimer laser at 193 nm. Molecules photodissociated were HCCBr, HCCCH₂Br, HCCCH₂Cl, CH₃Cl, C₂H₅Cl and i-C₃H₇Cl. The time-of-flight distributions of the photofragments were measured in order to study the primary processes and the dissociation dynamics. Generalizations consistent with the data are that atomic products (RX → R + X) result from direct dissociation of the CX repulsive singlet state, molecular elimination (RX → R′ + HX) is a result of a crossover to the ground state and triplet states are involved in the photodissociation of alkyne compounds.     

Synthesis of poison-frog alkaloids 237D, 207A, and two congeners of 235B' for evaluation to inhibitory effect of nicotinic acetylcholine receptors

Enantioselective synthesis of the poison-frog alkaloids 237D, 207A, and two congeners of 235B' has been achieved. The absolute stereochemistry of 237D was determined to be 5S, 8S, 9R by the present synthesis.     

A recyclable catalyst for asymmetric transfer hydrogenation with a formic acid-triethylamine mixture in ionic liquid

A novel task-specific ionic ligand with an imidazolium salt moiety was synthesized, and its catalytic ability and recyclability for asymmetric transfer hydrogenation of acetophenone derivatives with a formic acid-triethylamine azeotropic mixture in an ionic liquid [bmim][PF6] was examined.     

Fractal dimensions for diffusion-limited aggregation

A mean-field theory is proposed for fractal dimensions of diffusion-limited aggregates grown on a substrate surface of arbitrary dimensionality. The results are in good agreement with those of the computer simulations for all dimensionalities.     

Study of decay mechanisms in B--->Lambdac+ppi- decays and observation of low-mass structure in the Lambdac+p system

Using a sample of 152 x 10(6) BB pairs accumulated with the Belle detector at the KEKB e+e- collider, we study the decay mechanism of three-body charmed decay B- --> Lambdac+ ppi-. The intermediate two-body decay B--->Sigmac (2455)0 p is observed for the first time with a branching fraction of (3.7 +/- 0.7 +/- 0.4 +/- 1.0) x 10(-5) and a statistical significance of 8.4sigma. We also observe a low-mass enhancement in the (Lambdac+p) system, which can be parametrized as a Breit-Wigner function with a mass of (3.35(-0.02)(+0.01) +/-0.02) GeV/c2 and a width of (0.07(-0.03)(+0.04) +/-0.04) GeV/c2. We measure its branching fraction to be (3.9(-0.7)(+0.8) +/- 0.4 +/- 1.0) x 10(-5) with a statistical significance of 6.2sigma. The errors are statistical, systematic, and that of the Lambdac+-->pK- pi+ decay branching fraction.