Ionization of Acetylacetone in Me2SO—Water Mixtures. Reactivity—Selectivity Principle or Principle of Imperfect Synchronization?

Rate constants for the reversible deprotonation of acetylacetone were measured in carboxylate and amine buffers in water and in 50%, 90% and 95% Me₂SO at 20°C. The Brønsted plot for the carboxylate ions is curved in the Me₂SO—water mixtures, but straight in water. The curvature is in the direction predicted by the Reactivity—Selectivity Principle (RSP). However, the Brønsted plot for the reaction with primary amines is straight in all solvents. This suggests that the curvature observerd with the carboxylate ions is caused by loss of solvation of the base; this loss of solvation is ahead of bond formation in the transition state rather than being a manifestation of the RSP. (Note that all Brønsted plots are based on pK_a values measured in the respective solvents.) The intrinsic rate constant (k₀) for proton transfer increases with the addition of Me₂SO, and more so with the carboxylate buffers than with the amines. This increase in k₀ is attributed to delayed solvation of the developing enolate ion in the transition state; with the carboxylate buffers, an additional factor is the early loss of solvation of the base. The various solvation effects observed in this study can all be understood in the context of the Principle of Imperfect Synchronization (PIS).     

A new mumps virus lineage found in the 1995 mumps outbreak in western Switzerland identified by nucleotide sequence analysis of the SH gene

We determined the nucleotide sequence of the SH gene its flanking regions over a range of 380 nucleotides for three distinct mumps virus (MUV) isolates. Two isolates from the 1992 mumps epidemic in Western Switzerland and one MUV isolated in 1995 in the same geographic area have been analyzed and compared to 16 recently published SH nucleotide sequences and their presumed amino acid sequences. The nucleotide sequences from the 1992 MUV isolates were identical and closely related to two MUV strains from Eastern Switzerland and strains from the U.K. The MUV isolated in 1995 is clearly different from all other strains.     

IDENTIFICATION OF NITROGEN COMPOUNDS AND THEIR EVOLUTIONDURINGAGEING NABSENCE ANDPRESENCE OF ADDITIVES EFFICIENCYOFHYDROTREATMENT

As established by several previous works, nitrogen compounds play a prominent role in the evolution of middle distillates containing cracked components, particularly regarding sediment formation and color evolution.

In a first part, this paper describes and compares stability properties of fuel blends using both an accelerated ageing method at 120°C (248°F ) and long term storage methods at 43°C(110°F) -ASTM 0 4625 - and at ambient temperature. Effectiveness of stabilizing additives is also evaluated. In mixtures containing LCOs, insoluble products are formed progressively during ageings, more or less rapidly according to the chemical constitution of the mixtures.

Then, it reports the complete identification of nitrogen compounds using gas chromatography equipped with a selective nitrogen detector and mass spectrometry showing that in light cycle oils, alkyl indoles and carbazoles are the main families.

Evolution of these compounds was followed kinetically during ageings in absence and presence of additives and alkyl indoles appeared as the moat evolutionary.

It appeared that some additives avoided evolutions of alkyl indoles without preventing sediment formation and color evolution. Oxidation mechanism involving nitrogen compounds should not be the only one to explain the storage evolutions of middle distillates.

Hydrotreatment converts all the alkyl indoles of LCO and prevents coloration end deposits in the storage of the mixtures of steaight-run distillates and LCOs.     

Determination of the content of wax esters in some sea foods and their molecular composition. A comparison with ω-3 enriched wax esters

Wax esters enriched in ω-3 fatty acids have been recently shown to be readily absorbed by rats after dietary supplementation. Wax esters are less prone to oxidation and can be better formulated than liquid ω-3 derivatives. All these characteristics suggest a possible use of wax esters enriched in ω-3 as food supplements. However, some naturally occurring wax esters are defined as scarcely digestible (jojoba oil, spermaceti). On the other hand, wax esters have been found in several sources of marine origin, which can enter normal foodstuff. In order to better understand the digestibility of wax esters, we have analysed some foods from marine sources. The content of triglycerides and wax esters of the foods has been determined. Moreover, wax esters have been analysed for their composition in alcohols and fatty acids. Wax esters have been shown to be a part of the neutral lipid extract of the foods analysed. Their content, if compared with the content in triglycerides, shows striking differences. In the case of two botargo preparations, it has been shown that wax esters are more than 90% of the total neutral lipid extract. The content of fatty acids and alcohols found in the foods analysed is consistent with published data.     

Physical map of the D6S149-D6S193 region on chromosome 6Q27 and its involvement in benign surface epithelial ovarian tumours

A detailed long range restriction map of the region defined by markers D6S149 and D6S193 on chromosome 6q27 has been constructed. This was achieved by YAC cloning and contig assembling of the same region. Seven YAC clones were found to span the almost 1000 Kb region flanked by the two markers which on the genetic map resulted to be 1.9 cM apart. With some of the characterized YAC clones we undertook a molecular cytogenetic analysis of 20 benign ovarian tumors. The rationale for this was the recent mapping to a region of chromosome 6q27, flanked by markers D6281 and D6S133, of a locus for the SV40-mediated immortalization of human cells (SEN6 gene). Noteworthy we found that the the D6S149-D6S193 region (comprised in the larger D6S281-D6S133 physical interval) was altered in all samples analysed adding support to the occurrence of a immortalization step in this type of tumors.     

Storage life of frozen salmonoids Effect of light and packaging conditions on carotenoid oxidation and lipid oxidation

Summary The combined effect of oxygen transmission of packaging material and of exposure to light with different spectral distribution on the oxidative degradation of carotenoids and lipids in frozen salmonoids has been characterized in a storage experiment with steaks of rainbow trout. The degradation of the carotenoid astaxanthin, as followed by HPLC analysis and tristimulus colorimetric measurement, was sensitive to the radiant flux density of UV light and less sensitive to the oxygen transmission rate of the packaging material, in agreement with previous findings for photooxidation of carotenoids in food model systems. This is in contrast to the lipid oxidation, which was found to be dependent on the accessability of oxygen rather than on exposure to UV light. Formation of peroxides in the product culminated after 3 months of storage (up to 8.4 mEq kg^–1 oil), and preceded the formation of thiobarbituric-acid-reactive substances. The product in packaging material with a high oxygen transmission rate (60 cm³ m^–2 bar^–1 per 24 h) reached a level of approximately 5 mol malonaldhyde/kg^–1 product, when stored exposed to standard fluorescent light or fluorescent light with a high UV component. Rancid taste was not detected by sensory evaluation for any of the products after 6 months of storage, whereas a bitter taste was noted for the product exposed to UV light.

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Die Haltbarkeit von Lachsforellen Einfluß von Licht und Verpackung auf die Carotenoid- und Fettoxydation

Zusammenfassung Der kombinierte Effekt von Sauerstoffdurchgang durch Verpackungsmaterial und der Lichteinwirkung verschiedener spektraler Verteilung auf den oxidativen Abbau der Carotinoide und Fette in gefrorenen Lachsforellen wurde in einem Lagerungsversuch untersucht. Der Abbau des Carotenoids Astaxanthin wurde mit HPLC undTristimulus-Calorimetrie beobachtet, und war empfindlich gegenüber UV-Licht und weniger empfindlich gegenüber der Sauerstoffdurchlässigkeit der Verpackung, was mit früheren Ergebnissen für Photooxidation der Carotinoide in Modellsystemen übereinstimmt. Dies widerspricht der Fettoxidation, die mehr von Sauerstoffzugang abhängig ist als von der Entwicklung des UV-Lichtes. Die Bildung von Peroxiden des Produktes kuliminierte nach 3monatiger Lagerung (bis 8,4 meq/kg Öl) und ging der Bildung von Thiobarbitursäure-aktiven Substanzen voraus. Das Produkt im Material mit hohem Sauerstoffdurchgang (60 cm³ m^–2 bar^–1 pro 24 h), das bei normalen fluorescierendem Licht oder bei fluorescierendem Licht mit hohem UV-Anteil aufbewahrt wurde, erreichte einen TBS-Wert von ungefähr 5 mol Malonaldehyd/kg Fleisch. Ein ranziger Geschmack wurde durch sensorische Bewertung nach 6monatiger Lagerung nicht erkannt, wohl aber ein bitterer Geschmack bei dem UV-Licht ausgesetzten Proben.

     

Characterisation of three different impellers using the LDV-technique

A characterisation of three commonly used impellers was made in this study by measuring local mean velocities and the fluctuations of these velocities with the LDV technique. The data was used to estimate volumetric flow, velocity fluctuations and turbulent intensity in the impeller region of the tank. The impellers investigated were a high flow impeller, a pitched blade turbine and a Rushton turbine. The cylindrical vessel used was made of Perspex, had a dished bottom (DIN 28013), was equipped with four baffles and had an inner diameter of 0.45 m. It was found that the bulk velocities could be scaled with the tip-speed of the impeller (ND). The flow rate at constant impeller speed increased in the order high flow impeller — Rushton turbine — pitched blade turbine. The corresponding order for the turbulence fluctuation is: high flow impeller — pitched blade turbine — Rushton turbine. The velocity profile of the flow out from the high flow impeller was furthermore, not as smooth as could be expected.     

The Influence of Glow and Afterglow Cold Plasma Treatment on Biochemistry,Morphology, and Physiology of Wheat Seeds

Cold plasma (CP) technology is a technique used to change chemical and morphological characteristics of the surface of various materials. It is a newly emerging technology in agriculture used for seed treatment with the potential of improving seed germination and yield of crops. Wheat seeds were treated with glow (direct) or afterglow (indirect) low-pressure radio-frequency oxygen plasma. Chemical characteristics of the seed surface were evaluated by XPS and FTIR analysis, changes in the morphology of the seed pericarp were analysed by SEM and AFM, and physiological characteristics of the seedlings were determined by germination tests, growth studies, and the evaluation of α-amylase activity. Changes in seed wettability were also studied, mainly in correlation with functionalization of the seed surface and oxidation of lipid molecules. Only prolonged direct CP treatment resulted in altered morphology of the seed pericarp and increased its roughness. The degree of functionalization is more evident in direct compared to indirect CP treatment. CP treatment slowed the germination of seedlings, decreased the activity of α-amylase in seeds after imbibition, and affected the root system of seedlings.     

Real time identification of discrete event systems using Petri nets

The paper defines the identification problem for Discrete Event Systems (DES) as the problem of inferring a Petri Net () model using the observation of the events and the available output vectors, that correspond to the markings of the measurable places. Two cases are studied considering different levels of the system knowledge. In the first case the place and transition sets are assumed known. Hence, an integer linear programming problem is defined in order to determine a modelling the DES. In the second case the transition and place sets are assumed unknown and only an upper bound of the number of places is given. Hence, the identification problem is solved by an identification algorithm that observes in real time the occurred events and the corresponding output vectors. The integer linear programming problem is defined at each observation so that the can be recursively identified. Some results and examples characterize the identified systems and show the flexibility and simplicity of the proposed technique. Moreover, an application to the synthesis of supervisory control of systems via monitor places is proposed.