Observation of magnetic order of Cu-moment aroundx=0.12 in La2−x Ba x CuO4 and La2−x sr x CuO4 by μ+SR

Zero field positive muon spin rotation method ( ⁺SR) is applied on La_2–x Sr _x CuO₄ around forx=0.12 at which the high-T _c superconductivity (SC) is suppressed. The magnetically ordered state of Cu-moments, which is not a spin glass state but an antiferromagnetic like state, appears below 15 K for 0.105x0.120. The magnetic phase boundary is very similar to the one of the La_2–x Ba _x CuO₄ in which the structural transition from the low temperature orthorhombic (LTO) phase to the low temperature tetragonal (LTT) phase is observed aroundx=0.12. The present study suggests that there is no big difference of the electronic state of the CuO₂ plane between the La-Ba system and the La-Sr system and that the magnetic ordering of Cu-moments plays an important role for the suppression of the high-T _c SC aroundx=0.12 in both of the systems, although the LTO-LTT structural transition has not been observed yet in the La-Sr system.     

Direct catalytic asymmetric Michael reaction of hydroxyketones: asymmetric Zn catalysis with a Et2Zn/linked-BINOL complex

Full details of our direct Michael addition of unmodified ketones using new asymmetric zinc catalysis are described. Et(2)Zn/(S,S)-linked-BINOL complexes were successfully applied to direct 1,4-addition reactions of hydroxyketones. The first generation Et(2)Zn/(S,S)-linked-BINOL 1 = 2/1 system was effective for 1,4-addition of 2-hydroxy-2'-methoxyacetophenone (3). Using 1 mol % of (S,S)-linked-BINOL 1 and 2 mol % of Et(2)Zn, we found that a 1,4-addition reaction of beta-unsubstituted enone proceeded smoothly at 4 degrees C to afford products in high yield (up to 90%) and enantiomeric excess (up to 95%). In the case of beta-substituted enones, however, the first generation Et(2)Zn/(S,S)-linked-BINOL 1 = 2/1 system was not at all effective. The second generation Et(2)Zn/(S,S)-linked-BINOL 1 = 4/1 with MS 3A system was developed and was effective for various beta-substituted enones to afford products in good dr, yield (up to 99%), and high enantiomeric excess (up to 99% ee). With the Et(2)Zn/1 = 4/1 systems, catalyst loading for beta-unsubstituted enone was reduced to as little as 0.01 mol % (substrate/chiral ligand = 10 000). The new system was also effective for 1,4-addition reactions of 2-hydroxy-2'-methoxypropiophenone (9) to afford chiral tert-alcohol in high enantiomeric excess (up to 96% ee). Mechanistic investigations as well as transformations of the Michael adducts into synthetically versatile intermediates are also described.     

MYCOCHROME SYSTEM AND CONIDIAL DEVELOPMENT IN CERTAIN FUNGI IMPERFECTI

Abstract. A photoreceptor system, “mycochrome”, is involved in a blue and near UV reversible photo-reaction which in turn plays an important role in the photocontrol of conidial development in Alternaria tomato, Botrytis cinerea and Helminthosporium oryzae. Conidial development was controlled by alternating exposures to blue and near UV light with the final response being determined by the final light received. When the final light was near UV a conidium developed; when it was blue, conidiation was inhibited and a “sterile” conidiophore was formed. The effects of the two lights were alternatively reversible. Blue and near UV reversible photoreaction was also found in a light-minus-dark difference spectrum of an intracellular particulate fraction isolated from dark-grown mycelia of A. tomato, and two pigments, P_B (blue absorbing type) and P_NUV (near UV absorbing type), were contained in that photoreaction. P_B was tightly bound to the particulate fraction and P_NUV was either soluble in the cytoplasm or very loosely bound to the particulate fraction. Blue and near UV reversible photoreaction occurred only under the coexistence of P_B and P_NUV. That is, a dip in the near UV region and peak absorbance in the blue region was induced by irradiation with near UV light; however, both conditions were partially dissipated with a subsequent irradiation of blue light. These absorbance changes were revers-ibly repeated by alternating doses of blue and near UV light. When molecular oxygen was introduced after exposure to near UV light, peak absorbance in the blue region rapidly disappeared, and these absorbance changes were repeatedly reversible. Similar results were obtained by treatment with sodium hydrosulfite and molecular oxygen. Thus, it was concluded that the mycochrome system suggested in photo-conidiation was consistent with certain active substances showing blue and near UV reversible absorbance changes and caused by photooxidation reduction reaction.     

An implicit function theorem: Comment

In Ref. 1, Jittorntrum proposed an implicit function theorem for a continuous mappingF:R ⁿ ×R ^m R ⁿ, withF(x ⁰,y ⁰)=0, that requires neither differentiability ofF nor nonsingularity of _x F(x ⁰,y ⁰). In the proof, the local one-to-one condition forF(·,y):A R ⁿ R ⁿ for ally B is consciously or unconsciously treated as implying thatF(·,y) mapsA one-to-one ontoF(A, y) for ally B, and the proof is not perfect. A proof can be given directly, and the theorem is shown to be the strongest, in the sense that the condition is truly if and only if.     

Photochemical study of [3(3)](1,3,5)cyclophane and emission spectral properties of [3n]cyclophanes (n = 2-6)

Thephotochemical reaction of [3(3)](1,3,5)cyclophane 2, which is a photoprecursor for the formation of propella[3(3)]prismane 18, was studied using a sterilizing lamp (254 nm). Upon photolysis in dry and wet CH2Cl2 or MeOH in the presence of 2 mol/L aqueous HCl solution, the cyclophane 2 afforded novel cage compounds comprised of new skeletons, tetracyclo[6.3.1.0.(2,7)0(4,11)]dodeca-5,9-diene 43, hexacyclo[6.4.0.0.(2,6)0.(4,11)0.(5,10)0(9,12)]dodecane 44, and pentacyclo[6.4.0.0.(2,6)0.(4,11)0(5,10)]dodecane 45. All of these products were confirmed by the X-ray structural analyses. A possible mechanism for the formation of these photoproducts via the hexaprismane derivative 18 is proposed. The photophysical properties in the excited state of the [3n]cyclophanes ([3n]CP, n = 2-6) were investigated by measuring the emission spectra and determining the quantum yields and lifetimes of the fluorescence. All [3n]CPs show excimeric fluorescence without a monomeric one. The lifetime of the excimer fluorescence becomes gradually longer with the increasing number of the trimethylene bridges. The [3n]CPs also shows excimeric phosphorescence spectra without vibrational structures for n = 2, 4, and 5, while phosphorescence is absent for n = 3 and 6. With an increase in symmetry of the benzene skeleton in the [3(3)]- and [3(6)]CPs, the probability of the radiation (phosphorescence) process from the lowest triplet state may drastically decrease.     

Direct catalytic aldol-type reactions using RCH2CN

[reaction: see text] A copper fluoride-catalyzed cyanomethylation that can be applied to a wide range of ketones and aldehydes was developed using TMSCH(2)CN as a nucleophile. The reaction was extended to a conceptually more advanced copper alkoxide-catalyzed direct addition of alkylnitriles to aldehydes, which can act as a surrogate direct catalytic aldol reaction of esters. These reactions can be applied to the first catalytic enantioselective cyanomethylation of ketones and direct catalytic enantioselective cyanomethylation of aldehydes.     

BLUE and NEAR ULTRAVIOLET REVERSIBLE PHOTOREACTION IN THE INDUCTION OF FUNGAL CONIDIATION

Abstract— The effects of blue light and near UV light on the induction of conidiation in the fungus, Aliernuriu tomato, were investigated. Induction of conidiation was repeatedly controlled by alternating doses of near UV light and blue light. When the final light was near UV, conidiation was induced and conidia developed in the following darkness; when it was blue, the induction of conidiation was suppressed. When conidiation was induced by irradiation with a light mixed with near UV and blue, not only the time lag for inducing conidiation but also the amount of conidia formed were regulated by the fluence rates of both those lights.
Thus, 'mycochrome' is considered to function as a photoreceptor system in the induction of conidiation of this fungus.     

Photochemistry of 3-aryl-2-isoxazoline1

3-Phenyl-2-isoxazoline (1) was irradiated to give 4-phenyl-2-oxazoline (3), β-aminoaldehyde (14) and benzonitrile from its π-π^* singlet excited state. Several related derivatives afforded similar photoproducts on irradiation. The quantum yields of the photoreactions were dependent on the magnitudes of the singlet energies of the 2-isoxazolines. p-Cyanophenyl-2-isoxazoline (1c) formed a one-to-one photoadduct (22) with benzene.     

Metal-complex assemblies constructed from the flexible hinge-like ligand H2bhnq: structural versatility and dynamic behavior in the solid state

Novel metal-complex assemblies constructed from the flexible hinge-like ligand H(2)bhnq (H(2)bhnq=2,2'-bi(3-hydroxy-1,4-naphthoquinone)) have been synthesized. The X-ray crystal structures of these compounds reveal that four types of architectures are accessible by variation of the metal ions. In copper(II) compounds 1-3, the chelating bhnq(2-) ions bridge copper(II) centers to form one-dimensional zigzag chains. The chains of 1-3 are arranged by hydrogen-bonding interactions and stacking interactions to produce porous structures. Cobalt(II) and zinc(II) compounds 4 and 5 form one-dimensional helical chains. In 4 and 5, the crystal packing induces spontaneous resolution of the helical chains with chiral cavities formed perpendicular to the helices. Nickel(II) compounds 6 and 7 form cyclic tetramers. The fourth architecture, a dimer (compound 8), is obtained by the reaction of zinc(II) and bhnq(2-) in MeOH. In these compounds, changes of the dihedral angles and the metal-coordination mode of the bhnq(2-) ion induce the structural versatility. The assemblies of the zigzag chains of the copper(II) compounds exhibit reversible vapochromic behavior. UV/Vis, powder X-ray diffraction, EPR, and adsorption isotherm measurements indicate that this vapochromic behavior is based on the hinge-like flexibility of the bhnq(2-) ion.