Synthesis of optically active pheromones with an epoxy ring, (+)-disparlure and the saltmarsh caterpillar moth pheromone [(Z,Z)-3,6-cis-1-9,10-epoxyheneicosadiene]

(+)-Disparlure $\text{2}$, and the saltmarsh caterpillar moth pheromone enantiomers $\text{1}$ were synthesized and the stereochemistry of the naturally occurring $\text{1}$ was shown to be 9$\text{S}$, 1O$\text{R}$.     

Mononuclear five-coordinate molybdenum(IV) and -(V) monosulfide complexes coordinated with dithiolene ligands: reversible redox of Mo(V)/Mo(IV) and irreversible dimerization of [MoVS]- cores to a dinuclear [MoV2(mu-S)2]2- Core

A mononuclear five-coordinate molybdenum(IV) monosulfide complex, (Et4N)2[MoS(L)2] (L = cyclohexene-1,2-dithiolate) (1), was obtained and characterized by IR, UV-vis spectroscopic methods, and X-ray crystallography. 1 was oxidized by an equivalent ferrocenium cation to give the corresponding mononuclear molybdenum(V) complex, (Et4N)[MoS(L)2] (2), which was stable for a few minutes under a lower concentration than 0.3 mM and then further dimerized to (Et4N)2[Mo(L)2]2(mu-S)2 (3).     

Direct observation of adduct formation of alkyl and aromatic iodides with cl atoms using cavity ring-down spectroscopy

The reactions of Cl atoms with RI (R = n-C3H7, n-C4H9, cyclo-C6H11, C6H5, C6F5, and p-CH3C6H4) have been studied using cavity ring-down spectroscopy at a temperature range of 233-313 K and at 100 Torr total pressure of N2 diluent. Visible absorption spectra of the RI-Cl adducts were recorded at 440-520 nm at 263 K. The yields of the adducts were temperature-dependent. There was no discernible reaction of the adducts in the presence of 100 Torr of O2 at 263 K. Theoretical calculations were performed for C4H9I-Cl and C6H5I-Cl for quantitative explanation of the absorption spectra and the strength of the I-Cl bonds in the charge-transfer complexes. Evidence for the adduct formation following the reaction of Cl with C6H5Br was sought but not found at 440 and 520 nm.     

Kunzeanones A, B, and C: novel alkylated phloroglucinol metabolites from Kunzea ambigua

Three new metabolites, kunzeanones A (1), B (2), and C (3), along with three known compounds, cryptostrobin (4), (+)-spathulenol (5), and (−)-globulol (6), were isolated from the non-polar fraction of the dried leaves of Kunzea ambigua (Myrtaceae), which shows ichthyotoxicity toward a small fish, medaka. The structures of these new compounds were elucidated as condensates of alkylated phloroglucinol with methylflavanone and germacrane-type sesquiterpene, respectively, on the basis of spectral analyses including 1-D and 2-D NMR spectra. The stereochemistries of kunzeanones A and B were determined by X-ray crystallographic analysis. A sesquiterpene, (+)-spathulenol (5), among the isolates was characterized as the ichthyotoxic principle of the extract.     

Structure in the emission from pyrene evaporated films

Emission spectra and decay times of fluorescence of pyrene thin films prepared by evaporation onto substrates at liquid nitrogen temperature were measured. Structure in the emission from films warmed slowly up to higher temperature is found to the higher energy side of the excimer emission band. The decay time is about 410 ns at temperatures between 110 K and 210 K. But the emission from the film warmed up to a temperature above 210 K shows only the excimer emission. These results are discussed in relation to an amorphous structure in the pyrene evaporated thin film.     

Primal-dual algorithms and infinite-dimensional Jordan algebras of finite rank

We consider primal-dual algorithms for certain types of infinite-dimensional optimization problems. Our approach is based on the generalization of the technique of finite-dimensional Euclidean Jordan algebras to the case of infinite-dimensional JB-algebras of finite rank. This generalization enables us to develop polynomial-time primal-dual algorithms for ``infinite-dimensional second-order cone programs.' We consider as an example a long-step primal-dual algorithm based on the Nesterov-Todd direction. It is shown that this algorithm can be generalized along with complexity estimates to the infinite-dimensional situation under consideration. An application is given to an important problem of control theory: multi-criteria analytic design of the linear regulator. The calculation of the Nesterov-Todd direction requires in this case solving one matrix differential Riccati equation plus solving a finite-dimensional system of linear algebraic equations on each iteration. The number of equations and unknown variables of this algebraic system is m+1, where m is a number of quadratic performance criteria. Key words.polynomial-time primal-dual interior-point methods – JB-algebras – infinite-dimensional problems – optimal control problemsThis author was supported in part by DMS98-03191 and DMS01-02698.This author was supported in part by the Grant-in-Aid for Scientific Research (C) 11680463 of the Ministry of Education, Culture, Sports, Science and Technology of Japan.Mathematics Subject Classification (1991):90C51, 90C48, 34H05, 49N05     

Sonochemical preparation of composite nanoparticles of Au/gamma-Fe2O3 and magnetic separation of glutathione

We prepared Au/gamma-Fe2O3 composite nanoparticles by sonochemically reducing Au(III) ions employing no stabilizer in the aqueous solution to form stable Au nanoparticles and allowing them to attach onto the surface of gamma-Fe2O3 particles with an average size of 21 nm. Size of the formed Au nanoparticle depended on the initial concentration of Au(III) ions. The number of the Au nanoparticles, supported on each gamma-Fe2O3 particle was controlled by changing the relative amounts of Au(III) ions and gamma-Fe2O3 particles. The composite nanoparticles exhibited a high affinity with glutathione, a tripeptide with mercapto group so that separation and manipulation of glutathione in aqueous solutions could be performed by application of external magnetic field. Because the surfaces of the Au nanoparticles were not shielded by any stabilizers, or naked, sonochemically prepared Au/gamma-Fe2O3 composite nanoparticles seemed to show stronger affinity to the glutathione than those by the radiochemical method.     

Evolution of host-parasitoid network through homeochaotic dynamics

Host-parasitoid systems with evolving mutation rates are studied. By increasing the growth rate of hosts, the diversity of both species is maintained dynamically. For the lower growth rate, diversity is brought about by mere parasitism. The average mutation rate for parasites is elevated to a high value, while that for hosts is suppressed at a low level. For the higher growth rate, the mutation rates for both hosts and parasites are elevated to form a symbiotic cluster connected by on-going mutation. This symbiotic state is sustained through a chaotic oscillation keeping some coherency among species. For a flat landscape for hosts, dynamical clustering of oscillation is observed. Lyapunov spectra of such oscillations show that high dimensional chaos with small positive exponents underlies in the symbiotic state. This weak high dimensional chaos, termed "homeochaos," is essential to the maintenance of symbiosis in ecosystems.     

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.     

Optical-Optical Double Resonance Spectroscopy of the 1g(P1)-AΠ (1u)-XΣg Transition of I2

Optical-optical double resonance spectroscopy was used to study the 1_g(³P₁) ion-pair state of I₂ correlating to I⁻(¹S)+I⁺³P₁) at the dissociation limit. We gained access to the 1_g(³P₁) state though the A³Π (1_u) state in the (1+1) photon-excitation scheme. The pump laser excited the A³Π (1_u)-X¹Σ_g⁺ transition at a fixed frequency for state selection. The probe laser was scanned to detect the 1_g(³P₁)-A³Π (1_u) resonance by monitoring the ultraviolet emission from the 1_g(³P₁) state at 278 nm. The 1_g(³P₁) state was observed in a vibrational progression consisting of P and R doublets. An energy level analysis was carried out for the 1_g(³P₁) state in the 0≤ v ≤ 14 and 12≤J≤135 range, which led to a set of molecular parameters including the Ω-doubling constant. The Ω-doubling of the 1_g(³P₁) state was discussed by the pure precession model and interpreted to occur through the heterogeneous coupling with the 0_g⁻(³P₁) state correlating to the same ionic asymptote.