Cis-Unsaturated fatty acid products by hydrogenation with chromium hexacarbonyl

The use of Cr(CO)₆ was investigated to convert polyunsaturated fats intocis unsaturated products. With methyl sorbate, the same order of selectivity for the formation ofcis-3-hexenoate was demonstrated for Cr(CO)₆ as for the arene-Cr(CO)₃ complexes. With conjugated fatty esters, the stereoselectivity of Cr(CO)₆ toward thetrans, trans diene system was particularly high in acetone. However, this solvent was not suitable at elevated temperatures required to hydrogenatecis, trans- andcis, cis-conjugated dienes (175 C) and nonconjugated soybean oil (200 C). Reaction parameters were analyzed statistically to optimize hydrogenation of methyl sorbate and soybean oil. To achieve acceptable oxidative stability, it is necessary to reduce the linolenate constituent of soybean oil below 1–3%. When this is done commercially with conventional heterogenous catalysts, the hydrogenated products contain more than 15%trans unsaturation. By hydrogenating soybean oil with Cr(CO)₆ (200 C, 500 psi H₂, 1% catalyst in hexane solution), the product contains less than 3% each of linolenate andtrans unsaturation. Recycling of Cr(CO)₆ catalyst by sublimation was carried through three hydrogenations of soybean oil, but, about 10% of the chromium was lost in each cycle by decomposition. The hydrogenation mechanism of Cr(CO)₆ is compared with that of arene-Cr(CO)₃ complexes. Presented in part at Seventh Conference on Catalysis in Organic Syntheses, Chicago, Illinois, June 5–7, 1978.     

Performance of Methanol Oxidation Catalysts with Varying Pt:Ru Ratio as a Function of Temperature

This paper describes the effects of varying the Pt to Ru ratio in carbon-supported catalysts for methanol oxidation as a function of temperature. Previously these effects were studied in isolation, but now it is shown that the composition of a given catalyst as a function of temperature is extremely important for its activity towards methanol oxidation. Platinum rich 3:2 atomic ratio catalysts perform better than a 1:1 catalyst at 25 °C, where only Pt is believed to be active towards methanol dehydrogenation, since this process is a highly thermally activated process on Ru sites. This result is reversed at 65 °C, where the 1:1 catalyst displays much higher currents across the entire range of polarization. This may result from methanol dehydrogenation occurring on both Ru and Pt sites at higher temperatures. At an intermediate temperature, 45 °C, the 3:2 catalyst is seen to perform better at lower current values, while the 1:1 catalyst is superior at higher current densities, with the crossover occurring at 62 A g^–1. As a consequence, when designing fuel cell catalysts, the composition of the catalyst employed should be tailored with respect to the exact operating conditions, in order to promote optimum fuel cell performance.     

Hydrogenation of methyl sorbate and soybean esters with polymer-bound metal catalysts

New polymer-bound hydrogenation catalysts were made by complexing PdCl₂, RhCl₃·3H₂O, or NiCl₂ with anthranilic acid anchored to chloromethylated polystyrene. The Pd(II) and Ni(II) polymers were reduced to the corresponding Pd(O) and Ni(O) catalysts with NaBH₄. In the hydrogenation of methyl sorbate, these polymer catalysts were highly selective for the formation of methyl 2-hexenoate. The diene to monoene selectivity decreased in the order: Pd(II), Pd(O), Rh(I), Ni(II), Ni(O). Kinetic studies support 1,2-reduction of the Δ4 double bond of sorbate as the main path of hydrogenation. In the hydrogenation of soybean esters, the Pd(II) polymer catalysts proved superior because they were more active than the Ni(II) polymers and produced lesstrans unsaturation than the Rh(I) polymers. Hydrogenation with Pd(II) polymers at 50~100 C and 50 to 100 psi H₂ decreased the linolenate content below 3% and increasedtrans unsaturation to 10~26%. The linolenate to linoleate selectivity ranged from 1.6 to 3.2. Reaction parameters were analyzed statistically to optimize hydrogenation. Recycling through 2 or 3 hydrogenations of soybean esters was demonstrated with the Pd(II) polymers. In comparison with commercial Pd-on-alumina, the Pd(II) polymers were less active and as selective in the hydrogenation of soybean esters but more selective in the hydrogenation of methyl sorbate. Presented at ISF-AOCS Meeting, New York, April 1980.     

Asymmetric reverse osmosis and ultrafiltration membranes prepared from sulfonated polysulfone

The concept of solubility parameter, developed by Hansen, has been applied to the determination of solubility diagram of polysulfone and sulfonated polysulfone. Data showing the effect of various parameters such as thermodynamic quality of the solvent, casting solution composition and viscosity, solvent evaporation period and precipitation bath composition, on membrane structure and performance have been presented. By adjusting these parameters a wide variety of sulfonated polysulfone membranes useful for both ultrafiltration and reverse osmosis applications could be obtained.     

Inactivation of Staphylococcus hyicus lipase by hexadecylsulfonyl fluoride: evidence for an active site serine

The Staphylococcus hyicus lipase is an acyl hydrolase with broadsubstrate specificity including neutral glycerides and phospholipids.To obtain further insight into the mechanism of action of thisenzyme, we tested several sulfonyl fluorides as active site-directedinhibitors. The enzyme is resistant to the well-known serineprotease/esterase inhibitor phenylmethanesulfonyl fluoride (PMSF),but is rapidly inactivated by hexadecylsulfonyl fluoride. Thekinetics of inactivation were studied in Triton X-100 micelles.Inactivation is fast and the rate of inactivation is constantover the pH range where this lipase is active. Metal ions likeCa²⁺ and Sr²⁺ do not appreciably influence the rate of inactivation,although the enzymatic activity is significantly increased,suggesting a structural role for these ions. The S.hyicus lipasecontains a consensus sequence G-H/Y-S-X-G. Substitution by site-directedmutagenesis of this serine (Ser369) by a cysteine resulted ina mutant with only 0.2% residual activity. The activity of thismutant could not be inhibited with water-soluble sulfhydrylreagents either in the presence or absence of Triton X-100 micelles.In the presence of Triton X-100 micelles, inactivation of themutant occurred with 4-nitrophenylhexadecyl disulfide (t_1/2= 125 min) while the wild-type enzyme does not react at all.We conclude that Ser369 is the active site residue and thatin water this residue is inaccessible. Only after interfacialactivation Ser369 (or Cys369) becomes exposed and reacts withirreversible inhibitors.     

纳米粒子/环氧树脂复合材料的固化动力学研究

在纳米Al2O3、Si3N4、SiC填充环氧树脂复合材料体系中,纳米粒子表面活性及粒子与环氧树脂之间的相互作用影响着环氧树脂的固化过程.本文利用傅立叶红外光谱表征了纳米粒子与环氧树脂之间的化学作用情况,并利用差视扫描量热仪研究了不同纳米粒子/环氧树脂复合材料的固化动力学.结果表明,具有相对最强表面活性的纳米Al2O3粒子与基体之间的相互作用最强,同时该粒子对环氧树脂固化过程的促进作用最显著.     

The influence of training level on manual flight in connection to performance,scan pattern,and task load

This work focuses on the analysis of pilots’ performance during manual flight operations in different stages of training and their influence on gaze strategy. The secure and safe operation of air traffic is highly dependent on the individual performances of the pilots. Before becoming a pilot, he/she has to acquire a broad set of skills by training to pass all the necessary qualification and licensing standards. A basic skill for every pilot is manual control operations, which is a closed-loop control process with several cross-coupled variables. Even with increased automation in the cockpit, the manual control operations are essential for every pilot as a last resort in the event of automation failure. A key element in the analysis of manual flight operations is the development over time in relation to performance and visual perception. An experiment with 28 participants (including 11 certified pilots) was conducted in a Boeing 737 simulator. For defined flight phases, the dynamic time warping method was applied to evaluate the performance for selected criteria, and eye-tracking methodology was utilized to analyze the gaze-pattern development. The manipulation of workload and individual experience influences the performance and the gaze pattern at the same time. Findings suggest that the increase of workload has an increased influence on pilots depending on the flight phase. Gaze patterns from experienced pilots provide insights into the training requirements of both novices and experts. The connection between workload, performance and gaze pattern is complex and needs to be analyzed under as many differing conditions. The results imply the necessity to evaluate manual flight operations with respect to more flight phases and a detailed selection of performance indications.

     

Zur personellen Verankerung der IT-Funktion im Vorstand börsennotierter Unternehmen: Ergebnisse einer inhaltsanalytischen Betrachtung

On the Rate of Board Members with IT Responsibilities in Firms Listed on the Stock Exchange: Results of a Content Analysis: This article reports on a content analysis that investigates the rate of board members with IT responsibilities in firms listed on the stock exchange in the German speaking countries. Furthermore, the study ascertains the correlation of six factors – which become evident through content analysis – with the rate of board members with IT responsibilities. A total of 679 annual reports of German, Austrian, and Swiss corporations have been analyzed. The results show that in Germany and Switzerland 26 percent of the firms investigated have a board member with IT responsibilities, in Austria the rate is 23 percent. Additionally, the results show that turnover and number of employees are highly positively correlated with the rate of board members with IT responsibilities. Furthermore, the data show a correlation between industry and the rate of board members with IT responsibilities.     

Computing presentations for subgroups of polycyclic groups and of context-free groups

Algorithms for solving uniform decision problems for algebraic structures crucially depend on the chosen finite presentations for the structures under consideration. Rewriting techniques have been used very successfully to solve uniform decision problems, when the presentations considered involve finite, noetherian, and ()-confluent rewriting systems. Whenever the class of algebraic structures considered is closed under the operation of taking finitely generated substructures, then the algorithms for solving the uniform decision problems can be applied to the substructures as well. However, since these algorithms depend on the form of the presentations, this involves the task of constructing a presentation of a certain form for a substructure given a presentation of this form for the structure itself and a finite set of generating elements for the substructure.This problem, which has received a lot of attention in algebra, is here investigated from an algorithmic point of view. The structures considered are the following two classes of groups, which have been studied extensively before: the polycyclic groups and the context-free groups.Finitely generated context-free groups can be presented by finite, monadic, and -confluent string-rewriting systems. Due to their nice algorithmic properties these systems provide a way to effectively solve many decision problems for context-free groups. Since finitely generated subgroups of context-free groups are again contextfree, they can be presented in the same way. Here we describe a process that, from a finite, monadic, and -confluent string-rewriting system presenting a context-free groupG and a finite subsetU ofG, determines a presentation of this form for the subgroup U ofG that is generated byU. For finitely presented polycyclic groups we obtain an analogous result, when we use finite confluent PCP2-presentations to describe these groups.This work was performed while this author was visiting at the Fachbereich Informatik, Universität Kaiserslautern, during his sabbatical 1991/92     

Incremental value of prognostic testing in patients with known or suspected ischemic heart disease: a basis for optimal utilization of exercise technetium-99m sestamibi myocardial perfusion single-photon emission computed tomography

OBJECTIVES: This study assessed the incremental prognostic implications of normal and equivocal exercise technetium-99m (Tc-99m) sestamibi single-photon emission computed tomography (SPECT) and sought to determine its incremental prognostic value, impact on patient management and cost implications. BACKGROUND: The prognostic implications of Tc-99m sestamibi SPECT are not well defined, and risk stratification using this test has not been explored. METHODS: We studied 1,702 patients referred for exercise Tc-99m sestamibi SPECT who were followed up for a mean (+/- SD) of 20 +/- 5 months. Patients with previous percutaneous transluminal coronary angioplasty or coronary artery bypass surgery were excluded. The SPECT studies were assessed using semiquantitative visual analysis. Cardiac death and myocardial infarction were considered "hard" events, and coronary angioplasty and bypass surgery > 60 days after testing were considered "soft" events. RESULTS: Of the 1,702 patients studied, 1,131 had normal or equivocal scan results. A total of 10 events occurred in this group (1 cardiac death and 1 myocardial infarction [0.2% hard events]; 4 coronary angioplasty and 4 bypass surgery procedures [0.7% soft events]). The rates of hard events and referral to catheterization after SPECT were similarly low in patients with a low (< 0.15), intermediate (0.15 to 0.85) and high (> 0.85) post-exercise treadmill test (ETT) likelihood of coronary artery disease. With respect to scan type, patients with normal, probably normal or equivocal scan results had similarly low hard event rates. In the 571 patients with abnormal scan results, there were 43 hard events (7.5%) and 42 soft events (7.4%) (p < 0.001 vs. 1,131 patients with normal scan results for both). When the complete spectrum of scan responses was considered, SPECT provided incremental prognostic value in all patient subgroups analyzed. However, the nuclear scan was cost-effective only in patients with interpretable exercise ECG responses and an intermediate to high post-ETT likelihood of coronary artery disease and in those with uninterpretable exercise ECG responses and an intermediate to high pre-ETT likelihood of coronary artery disease. CONCLUSIONS: Normal or equivocal exercise Tc-99m sestamibi study results are associated with a benign prognosis, even in patients with a high likelihood of coronary artery disease. Although incremental prognostic value is added by nuclear testing in all patient subgroups, a testing strategy incorporating nuclear testing proved to be cost-effective only in the groups with an intermediate to high likelihood of coronary artery disease before scanning.