Determination of boron in nickel-base alloys by the dianthrimide method

The dianthrimide method for the determination of boron in iron and low-alloy steels may be applied to nickel-base materials. The sample is dissolved, without any loss of boron, by hydrochloric and sulphuric acids and the resulting boric acid determined spectrophotometrically with dianthrimide. Background corrections are necessary to compensate for the absorbance from ions such as nickel and iron.     

Fluorous synthesis of minor groove binding agents related to distamycin

Minor groove binding agents related to distamycin have been shown to target specific DNA sequences with high affinity. We report a new method for the preparation of these agents using fluorous synthesis in which the fluorous tag is located on what will become the cationic tail of the molecule. We demonstrate that fluorous synthesis yields both simple and complex polyamides in good yields and in high purity.     

Studies of the thermal degradation of acetaminophen using a conventional HPLC approach and electrospray ionization-mass spectrometry

The thermal degradation of acetaminophen is studied via conventional accelerated aging studies by initially thermally stressing the compound at temperatures between 160 degrees C and 190 degrees C and measuring the rate of decomposition by reversed-phase high-performance liquid chromatography. Rates of decomposition of the compound in the dry state and the activation energy for the process are determined and compared with previously published kinetic and thermodynamic data for the degradation of acetaminophen in solution. In addition, the thermal fragmentation of acetaminophen under electrospray ionization (ESI) conditions using an interface with a heated capillary inlet is studied and the apparent activation energy for this process also is characterized. A comparison of the data shows that acetaminophen is significantly more stable in the dry state than in solution. However, the gas-phase fragmentation of acetaminophen under ESI conditions occurs more readily than either dry- or solution-state degradation. Although the resulting electrospray fragmentation mimics the breakdown product that is formed when the compound undergoes either acid or base catalyzed hydrolysis in aqueous solutions, the mechanism that produces the fragment ion appears to involve a two-step process. Initially, the parent ion forms of the analyte are produced in the spray region of the interface followed by wall-catalyzed decomposition and re-ionization in the heated inlet capillary of the spectrometer.     

Synthesis of Sybstituted Isoxazoles and Pyrazoles Based on 1-Aryl-3,4,4-trichloro-3-buten-1-ones

3-Aryl-5-methylenehydroxyiminoisoxazoles were synthesized by reaction of 1-aryl-3,4,4-trichloro-3-buten-1-ones with hydroxylamine. Reactions of ketones with hydrazine provided pyrazole structures; therewith two pyrazole molecules underwent coupling affording 3-arylpyrazole-5-carbaldehyde azines.     

Molecular dynamics simulations of the mononuclear zinc-beta-lactamase from Bacillus cereus complexed with benzylpenicillin and a quantum chemical study of the reaction mechanism

Herein, we present results from MD simulations of the Michaelis complex formed between the B. cereus zinc-beta-lactamase enzyme and benzylpenicillin. The structural and dynamical effects induced by substrate-binding, the specific role of the conserved residues, and the near attack conformers of the Michaelis complex are discussed. Quantum chemical methods (HF/6-31G* and B3LYP/6-31G*) are also applied to study the hydrolysis reaction of N-methylazetidinone catalyzed by a monozinc system consisting of the side chains of the histidine residues (His86, His88, and His149) complexed with Zn-OH and the side chains of Asp90 and His210. From this model system, we built molecular-mechanics representations of the prereactive complex and transition state configurations docked into the active site. Linear-scaling semiempirical calculations coupled with a continuum solvent model were then performed on these static models. We propose that the experimental rate data for the B. cereus enzyme is compatible with a one-step mechanism for the hydrolysis of beta-lactam substrates in which His210 acts as a proton donor.     

Effects of various triamines on cell-free polypeptide synthesis of Escherichia coli and on growth of its polyamine auxotrophs

The effects of various synthetic triamines having a general structure, H2N(CH2)xNH(CH2)yNH2, where x = 2-5 and y = 2-8 (abbreviated, x-y; with 3-4 being spermidine itself), on poly(U)-directed polypeptide synthesis of Escherichia coli and on growth of its polyamine-requiring mutants were examined in comparison with those of spermidine. Except for 2-2 and 2-3, all of the triamines stimulated more or less polypeptide synthesis at suboptimal Mg2+ concentrations, but the Mg2+ concentration required for the maximal stimulatory effect was different for each triamine. The degree of maximal stimulation caused by 3-3 (norspermidine), 4-4 (homospermidine), or 4-5 was nearly comparable with that by spermidine. The acetylspermidines were inactive, however, they inhibited the spermidine-stimulated polyphenylalanine synthesis. Many of the triamines examined reduced the ratio of leucine to phenylalanine incorporation into polypeptides during poly(U)-directed translation, and the degree of this effect did not necessarily correspond with that of the stimulatory effect. Moreover, 2-4, 2-5, 3-3 and 4-4 could stimulate the growth of a polyamine auxotroph of E. coli, MA 261, as effectively as did spermidine. However, 3-3 was the only triamine which could fully replaced spermidine in promoting growth of a mutant strain, KK 101, which is more dependent on polyamines than MA 261. Thus, these results demonstrated that some synthetic triamines were as active as spermidine in eliciting these effects, and also that there were some differences among these effects in the structural requirement for triamine.     

Potential acting on the trapped electron

If the absorption of a trapped electron can be shown to correspond to bound—free transitions, it should be possible to calculate the potential acting on the trapped electron inversely from its absorption spectrum. In this paper we present the method of calculating the potential acting on a trapped electron from the observed absorption spectrum.     

Synthesis of 8,9-dialkoxy-substituted tetrahydrobenz[h] isoquinolines

6,7-Dimethoxy-2-naphthylethylamine, prepared by the diborane reduction of 6,7-dimethoxy-2-naphtlialeneacetamide, underwent a Pictet-Spengler cyclization to form 8,9-dimethoxy-1,2,3,4-tetrahydrobenz[h]isoquinoline. This compound is identical with that obtained by reduction of the corresponding dihydrobenzisoquinoline prepared from formamide cyclization. 6,7-Dialkoxy-2-naphthaleneacetic acids, the key intermediates for the preparation of these amides, were obtained from 6,7-dialkoxy-2-acetonaphthones by a modified Willgerodt reaction.     

Untersuchungen über die Oxydation von Butylbenzol in flüssiger Phase in Gegenwart von Kobalt- und Mangansalzen der Pyridincarbonsäuren

Zusammenfassung Es wurde der Einfluß der Kobalt- und Mangansalze der -, - und -Pyridincarbonsäuren auf die Luftoxydation von Rutylbenzol in flüssiger Phase untersucht. Dabei wurde festgestellt, daß das Kobaltpicolinat, Manganisonicotinat und Kobaltisonicotinat den Oxydationsverlauf zur Bildung von Carbonylverbindungen und Säuren lenken. Das Manganpicolinat weist ein selektives Oxydationsvermögen auf, vorwiegend zur Bildung von Estern.

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Liquid phase oxidation of butyl-benzene in presence of Co and Mn pyridine carboxylates

The influence of Co- and Mn-salts of -, - and -pyridinecarboxylic acids, resp., on the oxidation of butylbenzene by air has been studied. It has been found that the Co salt of picolinic acid, Mn and Co isonicotinate direct the oxidation process in favour of carbonyl compounds and acids. With the Mn salt of picolinic acid, the oxidation mainly gives esters.

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Mit 5 Abbildungen     

Public education in nuclear science at the Kyushu Museum of Energy in Japan

The Kyushu Museum of Energy, funded by the Kyushu Electric Power Company, Inc., was opened in September 1982. The planning and design were done by Dentsu, Inc., and the actual construction was shared among several construction and manufacturing companies. I was retained as the principal scientific advisor for the museum, both prior to its construction, throughhout the planning of the exhibits, and afterwards when it was opened to the public. This is an educational museum, which shows how people have developed and depended on energy and energy sources since the discovery of fire in prehistory. There are four major sections, devoted to fire itself, electricity, nuclear power by fission, and nuclear power by fusion. In addition, the museum will track visitors through the exhibits, in terms of The History of Energy as a beginning point for their tour, lead them through Present Energy Needs and Uses, and thence to Future Energy Developments and Needs. The museum is of a hands-on active display type design, with many large and attractive display panels, working models, pleasant mixes of sound, light, and images, and educational levels that encompass general public interest to semitechnical explanations that will satisfy the undergraduate with a technical, background. Visitors can not only operate the models themselves, but join in a variety of games based on energy consumption, usage, and needs. It is very much a participatory museum, and visitors are exposed to the many facets of day-to-day energy generation and consumption, as well as the estimated needs for the future, and possible ways to supply these needs. To date, there have been well over 200,000 visitors recorded. *** DIRECT SUPPORT *** A0653119 00004