D3h‐Symmetric Porphyrin‐Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One‐Nanometer‐Sized Cavity

The one‐step synthesis of D_3h‐symmetric cyclic porphyrin trimers 1 composed of three 2,2′‐[4,4′‐bis(methoxycarbonyl)]bipyridyl moieties and three porphyrinatozinc moieties was achieved from a nickel‐mediated reductive coupling of meso‐5,15‐bis(6‐chloro‐4‐methoxycarbonylpyrid‐2‐yl)porphyrinatozinc. Although cyclic trimers 1 were obtained as a mixture that included other cyclic and acyclic porphyrin oligomers, an extremely specific separation was observed only for cyclic trimers 1 when using columns of silica gel modified with pyrenylethyl, cyanopropyl, and other groups. Structural analysis of cyclic trimers 1 was carried out by means of NMR spectroscopy and X‐ray crystallography. Treatment of an η³‐allylpalladium complex with a cyclic trimer gave a tris(palladium) complex containing three η³‐allylpalladium groups inside the space, which indicated that the bipyridyl moieties inside the ring could work as bidentate metalloligands.     

Magnetic-field-induced valence transition in EuNi2(Si1−x Gex)2 in fields up to 500 T

The critical fields of the valence transition induced by a magnetic field in the EuNi₂(Si_1?x Ge_x)₂ (x=0.5–0.75) compound in an intermediate valence state are measured. The magnetic-field-induced valence transition is observed in the low-concentration range down to x=0.5. It is demonstrated that the critical field increases linearly with a decrease in the germanium concentration.     

Exponential decay rate of survival probability in a disastrous random environment

Summary. We study the exponential decay rate of the survival probability up to time t>0 of a random walker moving in Zopf; ^d in a temporally and spatially fluctuating random environment. When the random walker has a speed parameter κ>0, we investigate the influence of κ on the exponential decay rate λ(d,κ). In particular we prove that for any fixed d≥1, λ(d,κ) behaves like as logκ as κ↘0. Received: 21 May 1996 / In revised form: 2 February 1997     

The economical parameter survey program for long-term transient temperature distribution and stress analysis around the sodium level of the liquid metal fast breeder reactor

The thermal stress around the sodium level of the LMFBR reactor vessel, caused by the axial temperature distribution during heat-up and cool-down transient conditions, is one of the most important problems for a reactor vessel designer, especially in a conceptual design stage. Key parameters relating to plant operating transient conditions and reactor vessel main configuration should be settled carefully, thermal stresses not being allowed to exceed design stress limits. In order to examine the sodium level thermal stress easily and economically, a simple computer program for parameter survey has been developed. This program uses a one-dimensional Fourier series solution in transient temperature distribution analysis, and an analytical stress solution based on shell theory in stress value estimation. This paper presents a simplified and economical calculation method for the axial temperature distribution and stress value in the LMFBR operating transient conditions, and analysis examples obtained with this computer program.

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Zusammenfassung Der durch die axiale Temperaturverteilung während der Übergangsphase von Aufheizen und Abkühlen verursachte thermische Streß rund um den Natriumfüllstand des LMFBR-Reaktorkessels ist für den Reaktorkesselkonstrukteur, besonders im Entwurfstadiuni eines der wichtigsten Probleme. Die mit den transienten Operationsbedingungen der Anlage und der Gestaltung des Reaktorkessels in Beziehung stehenden Grundparameter müssen sorgfältig ermittelt werden, um zu verhindern, daß der thermische Streß die geplanten Streßgrenzen nicht überschreitet. Um den thermischen Streß um den Natriumfüllstand, leicht und ökonomisch zu bestimmen, wurde ein Komputerprogramm für die Parameterübersicht aufgestellt. In diesem Programm wird von einer eindimensionalen Fourrierreihe zur Analyse der transienten Temperaturverteilung und einer auf der Schalentheorie von Streßwertbestimmungen basierende analytische Lösung Gebrauch gemacht. Im vorliegenden Artikel werden eine vereinfachte und wirtschaftliche Berechnungsmethode für die axiale Temperaturverteilung und Streßwerte bei transienten Arbeitsbedingungen mitgeteilt und mit diesem Komputerprogramm ausgeführte Analysenbeispiele angegeben.

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Paper presented at the World Conference on Thermal Analysis, Madeira (Portugal) 1986.     

Practical asymmetric synthesis of (S)-MA20565, a wide-spectrum agricultural fungicide

A practical asymmetric synthesis of a wide-spectrum agricultural fungicide, (S)-MA20565 (1), is described. The convergent synthesis was achieved starting from commercially available 3-(trifluoromethyl)aniline (7) in 44% overall yield through five steps and 2-bromobenzaldehyde (9) in 48% overall yield through four steps, respectively. (S)-O-[1-(3-Trifluoromethylphenyl)ethyl]hydroxylamine (2), a key intermediate of 1, was prepared via ruthenium(II)-catalyzed asymmetric transfer hydrogenation of 1-(3-trifluoromethylphenyl)ethanone (6) followed by chlorination using methanesulfonyl chloride and oxyamination using potassium acetohydroxamate with high level of stereocontrol.     

TRIPLET STATE STUDIES OF FLAVlNS BY ELECTRON PARAMAGNETTC RESONANCE-III

Abstract— A continuation of studies is presented on the excited triplet state of flavins using EPR techniques. Detailed experiments are reported on the triplet state of flavin-mono-nucleotide (FMN) and flavin-adenine-dinucleotide (FAD). Action spectra of triplet yield are explained in terms of the optical absorption for FMN and FAD. Effects of light saturation, concentration quenching and oxygen on the triplet state are discussed. It is suggested that the rate constant k ₃ for the intersystem crossover from the excited singlet to the triplet state is increased by oxygen and quenchers such as KI. Detailed kinetic studies are presented on the formation of the triplet state.     

A new synthesis of enantiomerically pure α- and β-amino acid derivatives using aziridinyl anions

Optically active sulfinylaziridines having a 4-methoxyphenyl group on their nitrogen atom were synthesized from optically active 1-chloroalkyl p-tolyl sulfoxide and an imine derived from benzaldehyde and p-anisidine stereoselectively in good overall yields. The sulfinylaziridines were treated with ethylmagnesium bromide or tert-butyllithium to afford aziridinylmagnesiums or aziridinyllithiums, respectively, in quantitative yields. Cross-coupling of the aziridinylmagnesiums with iodoalkanes in the presence of Cu(I) iodide gave tri-substituted aziridines in high yields from which enantiomerically pure β,β-disubstituted β-amino acid derivatives were synthesized. A β-amino acid derivative having deuterium at the stereogenic center was also realized by this method. On the other hand, from the aziridinyllithium, enantiomerically pure quaternary phenylalanine and quaternary aspartic acid derivatives were synthesized.     

TRIPLET STATE STUDIES OF FLAVINS BY ELECTRON PARAMAGNETIC RESONANCE—I

Abstract— The triplet state of flavin derivatives and d-amino acid oxidase was observed by electron paramagnetic resonance at 77°K.
Flavin triplets (Δ m =± 2) originate from the isoalloxazine ring and are resonant at 1560 guass.The half-life of the FMN triplet in 1 N HCl is 15 nisec.This life-time is prolonged indirectly by the presence of paramagnetic species, such as oxygen or free radicals.
The flavin triplet state is pH dependent.In neutral solution the nlaximum triplet yield is obtained and the longest life-time is observed.The triplet state is affected by intra-and inter-molecular complex formation, FAD is partially quenched by indirectly substituted adenine.Tryptophan quenches completely the FMN triplet.The FAD triplet of d-amino acid oxidase is enhanced but the life-time is shortened relative to a pure FAD solution.     

Computational Analysis Reveals a Critical Point Mutation in the N-Terminal Region of the Signaling Lymphocytic Activation Molecule Responsible for the Cross-Species Infection with Canine Distemper Virus

Infection of hosts by morbilliviruses is facilitated by the interaction between viral hemagglutinin (H-protein) and the signaling lymphocytic activation molecule (SLAM). Recently, the functional importance of the n-terminal region of human SLAM as a measles virus receptor was demonstrated. However, the functional roles of this region in the infection process by other morbilliviruses and host range determination remain unknown, partly because this region is highly flexible, which has hampered accurate structure determination of this region by X-ray crystallography. In this study, we analyzed the interaction between the H-protein from canine distemper virus (CDV-H) and SLAMs by a computational chemistry approach. Molecular dynamics simulations and fragment molecular orbital analysis demonstrated that the unique His28 in the N-terminal region of SLAM from Macaca is a key determinant that enables the formation of a stable interaction with CDV-H, providing a basis for CDV infection in Macaca. The computational chemistry approach presented should enable the determination of molecular interactions involving regions of proteins that are difficult to predict from crystal structures because of their high flexibility.