Rhodium-Catalyzed Enantioselective Synthesis,Structures, and Properties of Single and Double Azahelicene-Like Molecules

The enantioselective synthesis of aza[6] and [7]helicene-like molecules have been achieved by the cationic rhodium(I)/axially chiral biaryl bisphosphine complex-catalyzed intramolecular [2+2+2] cycloaddition of cyanodiynes. This protocol was successfully applied to the diastereo- and enantioselective synthesis of an S-shaped double aza[6]helicene-like molecule with a high ee value of 89 %. Although no epimerization and racemization were observed in the double carbo[6]helicene-like molecule at 80 °C, epimerization and racemization of the double aza[6]helicene-like molecule proceeded at 80 °C. This double aza[6]helicene-like molecule showed good fluorescent quantum yields and chiroptical responses under both neutral and acidic conditions.     

Total Biosynthesis of Melleolides from Basidiomycota Fungi: Mechanistic Analysis of the Multifunctional GMC Oxidase Mld7

Mushroom terpenoids are biologically and chemically diverse fungal metabolites. Among them, melleolides are representative sesquiterpenoids with a characteristic protoilludane skeleton. In this study, we applied a recently established hot spot knock-in method to elucidate the biosynthetic pathway leading to 1α-hydroxymelleolide. The biosynthesis of the sesquiterpene core involves the cytochrome P450 catalyzing stepwise hydroxylation of the Δ⁶-protoilludene framework and a stereochemical inversion process at the C5 position catalyzed by short-chain dehydrogenase/reductase family proteins. The highlight of the biosynthesis is that the flavoprotein Mld7 catalyzes an oxidation-triggered double-bond shift accompanying dehydration and acyl-group-assisted substitution with two different nucleophiles at the C6 position to afford the Δ⁷-protoilludene derivatives, such as melleolide and armillarivin. The complex reaction mechanism was proposed by DFT calculations. Of particular importance is that product distribution is regulated by interaction with the cell membrane.     

On Harmonic Majorization of the Martin Function at Infinity in a Cone

This paper shows that some characterizations of the harmonic majorization of the Martin function for domains having smooth boundaries also hold for cones.     

Reduction of inelastic scattering effect by introduction of GalnAs/GalnP strain-compensated superlattice into multi-quantum barriers

The effect of inelastic scattering on the electron reflection in multi-quantum barriers (MQBs) has been examined using the damped resonant tunnelling model for the first time. The electron reflectivity in the virtual barrier region for unstrained GalnAs/InP MQB deteriorates below 100% by about 10% for phase relaxation time of 0.22ps. We propose a strain-compensated GalnAs/GalnP MQB which not only has virtual barrier 4 times as high as that of an unstrained MQB, but whose reflectivity deterioration is reduced to less than 5% in comparison with 10% for unstrained MQB for the same phase relaxation time. We have also successfully grown a Ga_0.25In_0.75As (1.5% compressive) well/Ga_0.25In_0.75P (1.2% tensile) barrier short-period superlattice with six wells by chemical beam epitaxy, which exhibits the possibility of fabrication of the strain-compensated MQBs.     

Memory effect on the glass transition in vulcanized rubber

The memory effect upon glassification is studied in the glass-to-rubber transition of vulcanized rubber with the strain as a controlling parameter. A phenomenological model is proposed, taking the history of the temperature and the strain into account, by which the experimental results are interpreted. The data and the model demonstrate that the glassy state memorizes the time course of strain upon glassification, not as a single parameter but as the history itself. The data also show that the effect of irreversible deformation in the glassy state is beyond the scope of the present model.     

Random Ising model in the magnetic field at T = 0: I. The distribution of the effective fields

The integral equation for the distribution function of the effective fields in the random Ising model in the finite external field is solved exactly at zero temperature in the one-dimensional case for 1) dilute ferromagnet, 2) dilute antiferromagnet and 3) ±J model. The ground state characteristics of these systems are obtained. In particular the effective fields in the ±J model are shown to have a triangular distribution in the zero external field limit.     

On maximal weights of Hadamard matrices

Let $\text{Ω}{}_{\mathrm{n}}$ denote the set of all Hadamard matrices of order n. For $\text{H ? Ω}{}_{\mathrm{n}}$, define the weight of H to be the number of 1's in H and is denoted by w(H). For a subset $\text{Γ ? Ω}{}_{\mathrm{n}}$, define the maximal weight of Γ as w(Γ) = max{w(H) | H?Γ}. Two Hadamard matrices are equivalent if one of them can be transformed to the other by permutation and negation of rows and columns, and the equivalence class containing H is denoted by [H]. In this paper, we shall derive lower bounds for w([H]), which are best possible for n ? 20. We shall also determine the exact value of $\text{w(Ω}{}_{32}\text{)}$.     

Zur stereospezifischen Poly merisation von Methylmethacrylat mit Grignard-Reagens

Ohne Zusammenfassung