Structure elucidation of AK-toxins,host-specific phytotoxic metabolites produced by alternaria kikuchiana tanaka

The structures of two host-specific phytotoxic metabolites, AK-toxin I and II, isolated from culture broth of Alternaria kikuchiana Tanaka (the fungus causing black spot disease of Japanese pear) were determined to be the ester consisting of N-acetyl-β-methyl-phenylalanine and 9,10-epoxy-8-hydroxy-9-methyl-2E, 4Z, 6E-decatrienoic acid ($\text{1}$) and its β-demethyl derivative ($\text{2}$).     

The role of the solvent in equilibrium and kinetic aspects of metal chelate extractions

Equilibria and kinetics for the extraction of nickel(II) and copper(II) by 2-hydroxy-5-nonylbenzophenone oxime (LIX 65N) in seven organic solvent systems were studied in order to test the validity of several hypotheses related to the role of the solvent in equilibrium and kinetic aspects of metal chelate extraction. For the nickel—LIX 65N system, the extraction constant is essentially independent of the solvent system, whereas for the copper—LIX 65N system, the extraction constant is not independent of solvent; this indicates that while the stoichiometry of the nickel chelate remains the same in all solvents, that of copper does not. The observed rate constant for the nickel—LIX 65N extraction was found to vary inversely with the LIX 65N distribution constant as predicted from a mechanism involving slow formation of the 1:1 complex. The observed reaction rate constant for the copper—LIX 65N varied inversely with the square of the distribution constant, also in accordance with the previously postulated mechanism of the slow formation of the 2:1 copper complex. This study, therefore, unequivocally eliminates the interfacial mechanism in favor of the homogeneous chemical reaction mechanism for the extraction of metal ions by LIX 65N, as well as by other similar high-molecular-weight extractants.     

Spin-crossover phenomenon of the assembled iron complexes with 1,2-bis(4-pyridyl)ethane as bridging ligand studied by Mössbauer spectroscopy

The transition temperatures between high- and low-spin states of the assembled spin-crossover complexes, Fe(NCX)₂(bpa)₂(guest) (X = S, Se, BH₃; bpa = 1,2-bis(4-pyridyl)ethane; guest = biphenyl, 2-nitrobiphenyl, diphenylmethane, or 1,4-dichlorobenzene), were compared with the Mössbauer parameters. The transition temperature increases when the QS value of Fe^II high-spin state becomes small. The transition temperature also increases by changing the anion from NCS to NCSe and then to NCBH₃.     

Analysis of visual perception of light emitting diode brightness in dense fog with various droplet sizes

Road signs must provide a conspicuous signal to a wide variety of drivers over a broad range of environmental and geometric conditions. Recently, there are an increasing number of applications in which light emitting diodes (LEDs) are used as the light source, including critical transportation signaling. In the presence of fog, the resulting visual signal is disturbed due to light scattering by airborne water droplets. By measuring LED brightness with human spectral sensitivity in various densities and various droplet sizes (10, 30, 50, and 100 μm), it is understood that the particle size distribution (fog droplet size) and density of fog does affect visibility in fog. The colored LEDs that contain a yellow component had high brightness evaluation, blue component had low brightness evaluation in all densities and different droplet sizes. The result in this paper can contribute to air and land traffic safety and the prevention of accidents.     

Synthesis of macrocyclic cage compounds by diamine-dihalide one-step coupling reaction

Macropolycyclic cage compounds were synthesized by a direct reaction between diamines and bis(bromomethyl) compounds. The procedure for constructing the polycyclic cage structure is simple and straightforward. The macropolycyclic compounds obtainable from this cyclization procedure are three-dimensional cage compounds, and any other isomers were not obtained except for two examples. Benzene, pyridine, and aliphatic units could be introduced into the cage structure. The macrocycles that have strong cation affinity were obtained as their potassium complexes.     

(15N) acetamide in polar solvents: Hindered internal rotation and intermolecular interactions

The ¹H spectrum of (¹⁵N)acetamide has been measured in dimethyl sulphoxide (DMSO), methyl propyl ketone (MPK), 1,3-dioxane, 1,4-dioxane, D₂O, acetonitrile and pyridine-d₅ at various temperature intervals within the range of 278–343 K. From the temperature dependence of the NMR spectra of the amide protons, the free energy of activation, ΔG^≠, for hindered rotation about the central C? N bond was determined by means of total line shape analysis in the four solvents DMSO, MPK and the two dioxanes. Observed values of ΔG^≠ (298 K) (72.7 in DMSO, 70.1 in MPK, 70.0 in 1,3-dioxane and 70.1 kJ mol¹ in 1,4-dioxane) were not very sensitive to the choice of solvent or concentration. The concentration dependence of the internal chemical shift between the amide protons was studied in MPK, D₂O, acetonitrile and pyridine-d₅. The free energy of activation and the internal chemical shift are discussed on the basis of solvent-amide and amide–amide specific hydrogen bonding interactions, and in comparison to the results of molecular orbital calculations.     

Picosecond study of energy transfer between rhodamine 6G and 3,3'-diethylthiacarbocyanine iodide in the premicellar region: förster mechanism with increased local concentration

The mechanism of enhancement in the energy transfer between rhodamine 6G and 3,3'-diethylthiacarbocyanine iodide by sodium lauryl sulfate in the premicellar region was studied by a picosecond laser technique. The Forster mechanism with an increased local concentration suggesting dye-rich induced micelle formation was concluded from the shape of the decay curve.     

Unsteady Falkner-Skan flow

Zusammenfassung Mittels des Differenzenverfahrens wurden instationäre, laminare Grenzschichten längs eines Keiles (von verschiedenen Keilwinkeln ) gerechnet, der plötzlich aus der Ruhe herausbewegt wird. Es ist bemerkenswert, daß im Fall >0.6 die Grenzschicht an der betreffenden Stelle der Keilwand bereits vor der Ankunft der an der Vorderkante entstehenden Störungen fast stationär wird, und daß, wenn die -Zahl sich dem Wert –0.1988 nähert, es doch eine beträchtliche Zeit braucht vom Vorüberziehen dieser Störungen bis zum Erreichen des stationären Zustandes der Grenzschicht.     

C-13 magnetic resonance studies of some papaveraceae alkaloids

The natural abundance ¹³C magnetic resonance spectra of some Papaveraceae alkaloids have been determined at 22·628 MHz employing the pulse Fourier transform technique. Several techniques were employed to aid in spectral assignments and it has been possible to make self-consistent assignments for all the resonances for these alkaloids. Evidence is presented for trans-annular interaction between the amino group and the carbonyl group situated across the ten-membered ring.