Synthesis and reactions of 4-isopropylidene-1-aryl-3-methyl-2-pyrazolin-5-ones

The reactions of 4-isopropylidene-1-aryl-3-methyl-2-pyrazolin-5-ones 4a-d were investigated under a variety of conditions. In the presence of thiols or piperidine, 4a-d failed to yield conjugate addition products, presumably due to the steric bulk provided by the two methyl substituents of the isopropylidene side chain. Reaction of 4a-d with hydrazine derivatives gave the 1-aryl-3-methyl-2-pyrazolin-5-ones 3a-d and isopropyl-hydrazones. Treatment of 4a with potassium cyanide yielded a stable conjugate addition product which exists as a mixture of tautomers in different solvents. Also, oxidation of 4a with hydrogen peroxide gave a spiroepoxide 22 , while m-chloroperbenzoic acid oxidation afforded both the spiroepoxide 22 , and a small quantity of a hydroxyspiroepoxide 23.     

Synthesis of some new o-thioazo ligands and evaluation of their metallochromic properties

The synthesis of several new o-thioazo derivatives of p-cresol and 2-naphthol is reported, as well as their spectral properties, acid dissociation constants, and potential as metallochromic reagents. All the ligands form complexes with CU²⁺ and Ni²⁺. o-Mercaptoazo complexes of Fe³⁺ and Cu²⁺ with molar absorptivities of 3.83 × 10⁴ and 3.58 × 10⁴ l.mole⁻¹ cm⁻¹, respectively, are described.     

Reactivity of DNA guanyl radicals with phenolate anions

Guanine bases are the most easily oxidized sites in DNA. Electron-deficient guanine species are major intermediates produced in DNA by the direct effect of ionizing radiation (ionization of the DNA itself) because of preferential hole migration within DNA to guanine bases. By using thiocyanate ions to modify the indirect effect (ionization of the solvent), we are able to produce these single-electron-oxidized guanine radical species in dilute aqueous solutions of plasmid DNA where the direct effect is negligible. The guanyl radical species produce stable modified guanine products. They can be detected in the plasmid by converting them to strand breaks after incubation with a DNA repair enzyme. If a phenol is present during irradiation, the yield of modified guanines is decreased. The mechanism is reduction of the guanine radical species by the phenol. It is possible to derive a rate constant for the reaction of the phenol with the guanyl radical. The pH dependence shows that phenolate anions are more reactive than their conjugate acids, although the difference for guanyl radicals is smaller than with other single-electron-oxidizing agents. At physiological pH values, the reduction of a guanyl radical entails the transfer of a proton in addition to the electron. The relatively small dependence of the rate constant on the driving force implies that the electron cannot be transferred before the proton. These results emphasize the potential importance of acidic tyrosine residues and the intimate involvement of protons in DNA repair.     

Spectra and structure of organogermanes: Part XX. Infrared and Raman spectra of (CH3)3GeNCO and (CH3)3GeNCS

The infrared and Raman spectra of gaseous and solid (CH₃)₃ GeNCO and solid (CH₃)₃GeNCS have been recorded over the frequency range 20–4000 cm^?1 . The Raman spectra of the liquids have also been recorded. Assignments of the normal modes have been made on the bases of band types, Raman depolarization values, and characteristic frequencies. Spectral data indicate that (CH₃)₃ GeNCO is non-linear in all phases and that (CH₃)₃GeNCS has a linear or quasi-linear heavy atom skeleton in the fluid phases.     

Evaluating the information content of a measure of plant output: An application to high-technology manufacturing

Commonly used measures of plant output have been criticized for their inability to provide information required to manage the dynamic operations of high-technology manufacturing plants. In this paper, we propose tests to evaluate the information content of a measure of plant output that is specifically directed at these issues. These tests are based on recent developments in DATA Envelopment Analysis (DEA), namely the Cone Ratio Envelopments. In this new application of DEA models, we shift the focus from Decision Making Units (DMUs) being evaluated to the DMUs that are being used to effect evaluations. The proposed tests are applied to evaluate the information contnet of a complexity adjusted measure of plant output, which we refer to as Total Net Die Equivalent (TNDE). Developed recently in the context of a high-technology manufacturing plant—a wafer fabrication plant of a merchant semiconductor manufacturing company-TNDE reflects the ongoing changes in product and process technologies, process flow characteristics, and volume of production. Evaluating the information content on joint criteria of recency and efficiency, the results of our tests, conducted over a 28-month period in the wafer fabrication plant,show that TNDE as a single aggregate (scalar) measure of plant output outperforms the two outputs from which it is synthesized. Thus, TNDE as a single measure of output can be used to provide an improved basis for planning a plant's future operations. En route to the development and application of the proposed tests, we illustrate how DEA concepts and models provide a rigorous and systematic basis for conducting ex post technology evaluation to guide continuous improvements in a plant's current operations.     

Sequence distribution and intramolecular excimer formation in styrene-acrylonitrile copolymers

Styrene-acrylonitrile copolymers, like many other copolymers containing styrene, exhibit both normal and excimer fluorescence. We have shown that the ratio of the excimer to monomer fluorescence intensities in random styrene-acrylonitrile copolymers is linearly dependent upon the concentration of styrene-styrene bonds in the copolymer. This observation is consistent with a photophysical model which allows the energy absorbed by styrene units to migrate freely along the copolymer chain. Some of the energy is emitted in the form of normal fluorescence; some of the energy, trapped by neighbouring styrene-styrene pairs suitably oriented to allow excimer formation, is emitted as excimer fluorescence. The fluorescence characteristics of acrylonitrile-styrene copolymers are contrasted with those of methyl methacrylate-styrene copolymers, in which the methylmethacrylate sequences are believed to present partial barriers to energy migration along the copolymer chains.