EPOXIDATION OF FUNCTIONALIZED OLEFINS OVER SOLID CATALYSTS

Heterogeneous catalytic epoxidation of functionalized olefins in the liquid phase has been reviewed, focusing on catalyst performance and its interrelation with the crucial parameters of the catalytic systems. Efficient catalysts include supported and mixed oxides, framework-substituted (“redox”) molecular sieves, layered-type materials, heterogenized homogeneous catalysts, and some others. Among the various substrates, allylic and homoallylic alcohols, and unsaturated carbonyl compounds have received most attention so far. The great variety of available catalysts enables selective epoxidation of most substituted olefins. The mechanistic understanding of heterogeneous catalytic epoxidation is still underdeveloped, rendering catalyst design rather empirical. A considerable potential for future development lies in the area of “heterogenization” of successful homogeneous catalysts especially for asymmetric epoxidation. Crucial requirements in the development of heterogeneous catalytic epoxidation catalysts are, besides good catalytic performance and cheap oxidant, recyclability and resistance to leaching of the active component. Some of the examples shown in the literature do not fulfill the latter requirement.     

The physical and physiological workload of refuse collectors

In order to secure a safer and healthy work situation, the heavy physical loads imposed on 23 refuse collectors (aged 26-54) working in the city of Haarlem, in The Netherlands, were studied in a series of three experiments between 1984 and 1987. The aims were respectively (1) to study the load for workers collecting dustbins or polythene bags; (2) to introduce changes to reduce the load to avoid exceeding the overload criteria by individual refuse collectors; and (3) to investigate the effects of interventions to improve the efficiency of refuse collecting. The maximal isometric lifting force (Fmax) and the maximal aerobic power (VO2max) of 23 refuse collectors were measured in the laboratory. Fmax was measured with an isometric dynamometer pulling with one arm from the floor; the mean value was 912 (+/- 127)N. VO2max was measured running on a treadmill; the mean value was 43.3 (+/- 0.8)ml O2 per kg body mass per min. The physical load on the oxygen transport system was measured through work analysis and by a continuous registration of the heart rate over three working days. Criteria for overload were set at a mean external load of 20% Fmax and a mean energy expenditure of 30% VO2max and an energy expenditure of 50% VO2max or more for a maximum of 60 min per day. Replacement of dustbins by polythene bags resulted in a 70% increase in the total amount of refuse collected, an increase in throwing frequency, but a lower mean load per throw, and no significant differences in the mean heart rate over the working day. When polythene bags were used the mean values did not exceed the overload criteria, but 39% of the individual collectors did have a workload that was too high with respect to one of the criteria. In the last experiment the collectors were advised to reduce their work load by (a) lifting no more than two bags at a time; (b) reducing their walking pace; and (c) taking more breaks. Although compliance with the recommendations was good, and the weight lifted and the walking speed decreased, the physiological load remained the same. This may have been caused by a 15% increase in the total amount of refuse that had to be collected at that time.     

Deprivation selectively modulates brain potentials to food pictures.

Event-related brain potentials (ERPs) were used to examine whether the processing of food pictures is selectively modulated by changes in the motivational state of the observer. Sixteen healthy male volunteers were tested twice 1 week apart, either after 24 hr of food deprivation or after normal food intake. ERPs were measured while participants viewed appetitive food pictures as well as standard emotional and neutral control pictures. Results show that the ERPs to food pictures in a hungry, rather than satiated, state were associated with enlarged positive potentials over posterior sensor sites in a time window of 170-310 ms poststimulus. Minimum-norm analysis suggests the enhanced processing of food cues primarily in occipito-temporo-parietal regions. In contrast, processing of standard emotional and neutral pictures was not modulated by food deprivation. Considered from the perspective of motivated attention, the selective change of food cue processing may reflect a state-dependent change in stimulus salience. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Resource pool management: Reactive versus proactive or let’s be friends

The consolidation of multiple workloads and servers enables the efficient use of server and power resources in shared resource pools. We employ a trace-based workload placement controller that uses historical information to periodically and proactively reassign workloads to servers subject to their quality of service objectives. A reactive migration controller is introduced that detects server overload and underload conditions. It initiates the migration of workloads when the demand for resources exceeds supply. Furthermore, it dynamically adds and removes servers to maintain a balance of supply and demand for capacity while minimizing power usage. A host load simulation environment is used to evaluate several different management policies for the controllers in a time effective manner. A case study involving three months of data for 138 SAP applications compares three integrated controller approaches with the use of each controller separately. The study considers trade-offs between: (i) required capacity and power usage, (ii) resource access quality of service for CPU and memory resources, and (iii) the number of migrations. Our study sheds light on the question of whether a reactive controller or proactive workload placement controller alone is adequate for resource pool management. The results show that the most tightly integrated controller approach offers the best results in terms of capacity and quality but requires more migrations per hour than the other strategies.     

Guest Diffusion in Binderless High‐Performance NaX Molecular Sieves

The pulsed field gradient (PFG) NMR technique is applied for exploring the diffusion behavior of guest molecules in binderless NaX beads in comparison with the zeolite powder employed for their production. With both probe molecules applied (water, n‐hexane), the diffusivities in the powder and the beads are found to essentially coincide as long as the diffusion path lengths are sufficiently small in comparison with the extension of the individual particles (crystallites) of the powder. With increasing diffusion path lengths, characteristic deviations become observable that can be attributed to the differences in long‐range mass transfer through the intercrystalline void volume of the bed of crystallites and within the individual beads of the binderless molecular sieve, respectively. With these studies, PFG NMR demonstrates its potentials for simultaneously recording mass transfer phenomena in both the micro‐ and macropores of commercially produced binderless molecular sieves.