Rationalization of anomalous nonlinear effects in the alkylation of substituted benzaldehydes

Anomalous nonlinear effects in the alkylation of substituted benzaldehydes with diethylzinc using aminoalcohol catalysts are rationalized in terms of a simple extension of the Noyori model to allow for nonthermodynamically controlled partitioning of the catalyst between monomeric and dimeric species. This work highlights the fact that catalyst composition in such systems may be influenced by substrate properties.     

Spontaneous emission in Ĉerenkov FEL devices: a preliminary theoretical analysis

Summary The main features of the spectral characteristics of the spontaneously emitted Ĉerenkov light in circular and rectangular wave guides filled with dielectric are discussed. The characteristics of the radiation emitted by an electron beam moving near and parallel to the surface of a dielectric slab are also analysed. Finally, the relevance of these results to a possible FEL-Ĉerenkov operation is briefly discussed.

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Riassunto In questo lavoro si discutono le caratteristiche dello spettro della radiazione Ĉerenkov, emessa in guide d'onde circolari e rettangolari riempite con dielettrico. Si analizzano inoltre le proprietà della radiazione emessa da un fascio di elettroni in moto in prossimità e parallelamente alla superficie di una ?slab? di dielettrico. Si discute, infine, brevemente, l'importanza di questi risultati per la realizzazione di un possibile FEL-Ĉerenkov.

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Резюме Обсуждаются основиые особенности спектральных характеристик спонтанного черенковского излучения в круговых и прямоугольных волноводах, заполненных диэлектриком. Также анализируются характеристики излучения, испущенного электронным пучком, движущимся вблизи и пораллелйно поверхности диэлектрической пластинки. В заключение, вкратце обсуждется применимость полученных результатов в возможных FEL-черенковских приборах.

     

Characterizing Hilbert cube manifolds by their homological structure

A hierarchy of disjoint ?ech carriers properties is introduced; and each is shown to be characteristic of ANR's whose products with 2-cells are Hilbert cube manifolds.     

Suicide substrates: mechanism-based enzyme inactivators

This review article defines suicide substrates as a class of irreversible inactivators of specific target enzymes where the target enzyme participates in its own destruction by catalytic unmasking of a latent functional group at some stage in the catalytic cycle of the enzyme. Criteria for evaluation of suicide substrates are presented. Then, examples of the various types of latent functional groups and their likely enzymic routes of activation are presented for both natural and synthetic compounds. These examples include gabaculine, secobarbital, allopurinol, clavulanate and penicillin sulfones, tranylcypramine, rhizobitoxin, fluoroalanine, 5-fluorodeoxyuridylate and mitomycin.     

The kinetics of pyrolysis of barrelene[1]: A concerted process on the C8H8 energy surface

The static vessel pyrolysis of bicyclo[2.2.2]octa-2,5,7-triene (barrelene) has been studied between 483 and 523 K. The products were acetylene and benzene (in equal quantities) with no other detectable C₈H₈ isomer (down to less than 1% of total). The time dependence fitted first-order kinetics, and the data are consistent with a homogeneous unimolecular reaction close to, if not at, its high-pressure limit at 0.25 torr. The rate constant was fitted to the Arrhenius equation These Arrhenius parameters are shown to imply a concerted single-step process. Alternative mechanisms are discussed and a comparison is made with the retro-Diels—Alder reactions of other bicyclo[2.2.2]octa-olefin systems.