Optimization of catalyst enantioselectivity and activity using achiral and meso ligands

The optimization of asymmetric catalysts for enantioselective synthesis has conventionally revolved around the synthesis and screening of enantiopure ligands. In contrast, we have optimized an asymmetric reaction by modification of a series of achiral ligands. Thus, employing (S)-3,3'-diphenyl BINOL [(S)-Ph(2)-BINOL] and a series of achiral diimine and diamine activators in the asymmetric addition of alkyl groups to benzaldehyde, we have observed enantiomeric excesses between 96% (R) and 75% (S) of 1-phenyl-1-propanol. Some of the ligands examined have low-energy chiral conformations that can contribute to the chiral environment of the catalyst. These include achiral diimine ligands with meso backbones that adopt chiral conformations, achiral diimine ligands with backbones that become axially chiral on coordination to metal centers, achiral diamine ligands that form stereocenters on coordination to metal centers, and achiral diamine ligands with pendant groups that have axially chiral conformations. Additionally, we have structurally characterized (Ph(2)-BINOLate)Zn(diimine) and (Ph(2)-BINOLate)Zn(diamine) complexes and studied their solution behavior.     

Dual wavelength lasers

Dual wavelength lasers are discussed, covering fundamental aspects on the spectroscopy and laser dynamics of these systems. Results on Tm:Ho:Er:YAG dual wavelength laser action (Ho at 2.1 μm and Er at 2.9 μm) as well as Nd:YAG (1.06 and 1.3 μm) are presented as examples of such dual wavelength systems. Dual wavelength lasers are not common, but there are criteria that govern their behavior. Based on experimental studies demonstrating simultaneous dual wavelength lasing, some general conclusions regarding the successful operation of multi-wavelength lasers can be made.     

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.