Synthesis,Characterization, and Reactivity of Lanthanide Complexes with Bulky Silylallyl Ligands

The synthesis of new lanthanide allyl complexes of enhanced stability and solubility in saturated hydrocarbons based on silyl-substituted allyl ligands is reported. Thus the potassium salt K(CH₂CHCHSiMe₃) ( 1 ) reacts with YCl₃ in tetrahydrofuran to give the tris-allyl complex Y(CH₂CHCHSiMe₃)₃ ( 2 ), while K(CH₂CHCHSiMe₂^tBu) ( 3 ) affords Y(CH₂CHCHSiMe₂^tBu)₃(THF)_1.5 ( 4 ). Slow re-crystallization of 4 from light petroleum in the presence of tert-butylcyanide led to multiple insertion to give the sec-amido complex Y{NHC(^tBu)(CH)₃SiMe₂^tBu}₂{η₂-NHC(^tBu)CH=CHCH₂SiMe₂^tBu)CH(CHCHSiMe₂^tBu)C^tBuNH}(THF)·(CH₃CH(Me)(CH₂)₂CH₃) ( 5 ), which was crystallographically characterized. The reaction of ScCl₃(THF)₃ with two equivalents of Li{1,3-C₃H₃(SiMe₃)₂} in tetrahydrofuran gives the bis-allyl complex {1,3-C₃H₃(SiMe₃)₂}₂Sc(μ-Cl)₂Li(THF)₂ ( 6 ), while the analogous reaction of K{1,3-C₃H₃(SiMe₃)₂} ( 7 ) with either LaCl₃ or YCl₃ in tetrahydrofuran affords the bis-allyl complexes MCl{1,3-C₃H₃(SiMe₃)₂}₂(THF)_x (8, M = La, x = 1; 9, M = Y, x = 0). An attempt to prepare the similar neodymium complex gave the mono-allyl complex NdI₂{1,3-C₃H₃(SiMe₃)₂}(THF)_1.25 ( 10 ). The reactions of 8 and 9 with triisobutyl aluminum in benzene-d₆ show allyl exchange between lanthanide and aluminum. Complexes 8 , 9 , and 10 have been tested with a variety of activator systems as catalysts for the polymerization of 1,3-butadiene.     

Stoichiometric dye-binding procedure for the determination of the reactive lysine content of soya bean protein

A new analytical method has been developed for the determination of the reactive lysine content of soya bean protein. The method is based on the reaction of the free basic groups of the protein with 1-phenylazo-2 naphthol-6,8 disulphonic acid. With regard to the stoichiometry of the procedure, it has been proved, contrary to earlier reports, that the basic amino acids, histidine, arginine and lysine, each combine with one mole of the dye. After acylation with propionic anhydride lysine alone loses its dye reactivity. The usefulness of the proposed method has been demonstrated by the determination of the reactive lysine content of several untreated, heat-treated and acid-treated soya bean samples. The results show that heat damage of about 5% in reactive lysine content can be measured in 1·5 h with good reproducibility.     

Porphyrin fluorescence in plasma of various types of porphyria

Fluorescence spectra of plasma porphyrin were measured in 6 patients with the acute intermittent porphyria (AIP), 30 patients with variegate porphyria (PV), 2 patients with hereditary coproporphyria, 2 patients with porphyria cutanea tarda, and in 6 patients with erythropoietic protoporphyria (EPP). It was found that the excitation and emission wavelengths at which maximum fluorescence is seen may help to diagnose and differentiate PV and EPP. In patients with AIP spectrum characteristic for porphyria of such a type was noted in all patients during the attack of disease and in only 33% of patients in remission. Fluorescence spectrum was normal in asymptomatic family members. In variegate porphyria spectrum with a characteristic maximum of fluorescence was noted in all patients during an attack and remission, and 62% of the asymptomatic family members.     

Self-calibration based on invariant view recognition: Dynamic approach to navigation

We extend a dynamic approach of behavior generation to the representation of spatial information. Two levels of dynamics integrate dead-reckoning, dominant far from home bases, and piloting, dominant near home bases. When the view-based piloting system recognizes a home base, visual place information recalibrates the dead-reckoning system, inverting the hierarchical ordering of the two dynamic levels by time scale inversion. Reference views taken at discrete home bases are recognized invariantly under rotation of views. This process yields compass information. Continuous translational information is obtained as a neural place representation built from view correlations with a scattered set of local views. This self-calibrating cognitive map couples into a dynamics of heading direction integrating the behaviors of obstacle avoidance and target acquisition. Targets can be designated in terms of the cognitive map. We demonstrate the dynamical model in simulation.     

Design optimization of supersonic jet pumps using high fidelity flow analysis

Supersonic jet pumps are simple devices with no moving parts, where a high velocity (primary) flow is used to pump a second fluid. In this paper, Computational Fluid Dynamics (CFD) is combined with an optimization framework in order to develop a tool for the rapid generation of jet pump designs. A key feature of the problem formulation is the transformation of the jet pump design parameters in terms of geometric ratios. This approach dramatically reduces the number of unrealistic designs covered by the Design of Experiments. Optimal Latin Hypercubes for surrogate model building and model validation points are constructed using a permutation genetic algorithm and design points are evaluated using CFD. Surrogate models of primary and entrained flow rates are built using a Moving Least Squares approach. A series of optimizations for various pump sizes are performed using a genetic algorithm and Sequential Quadratic Programming, with responses calculated from the surrogates. This approach results in a set of optimized designs, from which pumps for a wide range of flow rates can be interpolated.     

Thixoforging of continuous fiber-reinforced AlSi/AlMg-alloys

High strength in combination with low density is the key features for lightweight constructions in automotive and aerospace applications. Tailor-made fiber reinforcements in light-metal matrices could help to achieve this goal. However, the integration of fibers with conventional casting-route manufacturing techniques like squeeze casting or diffusion bonding restricts the component geometry and results in elevated process cost due to long cycle times and the need of additional fiber coatings. In the center of competence for casting and thixoforging Stuttgart (CCT), new processes for manufacturing metal matrix composites are developed. Long-fiber reinforced Al–Si alloys and components are produced by thixoforging of laminates made of alternating metal matrix layers and carbon fiber fabrics. This paper illustrates the manufacturing technology and first experimental results with special focus on fiber penetration and infiltration behavior and also on the formation of fiber-matrix interface to analyze fiber damage by mechanical or chemical attack.     

Isobutylene polymerization in the presence of t-BuCl/SnCl4

Summary The effect of tert-butyl chloride in the polymerizations of isobutylene carried out in the presence of SnCl₄ in dichloromethane at temperatures-20°C and-78°C was investigated. Synthesized polyisobutylene samples showed a bimodal molecular weight distribution (MWD) and it was found that the weight content of the lowermolecular weight (LMW) fraction increased with increasing t-BuCl concentration in the polymerization mixture. The effect of ageing of the initiation mixture t-BuCl/SnCl₄ in CH₂Cl₂ prepared in advance on MWD of the PIB samples was also studied. Ageing of the initiation system supports the formation of the LMW fraction and this oily PIB is the only product of the polymerization at-20°C, .     

A new variety of low-linolenic rapeseed oil; Characteristics and room-odor tests

Two Canadian rapeseed oils, “Westar” and “low-linolenic”, supplied by the Canola Council were studied and compared with a French rapeseed. The linolenic acid content of the low-linolenic variety is about 3%. This drop in the C18∶3 is completely compensated for by an increase in the C18∶2. Seventy-two percent of the triglycerides with at least one linolenic chain disappeared. A strong increase in the OOL and OLL was observed. The room-odor tests showed that the “low-linolenic” had a significantly higher odor score than the French rapeseed and the “Westar”, both of these being very similar. A fruity odor dominated in the “low-linolenic”, and the fishy painty odors were particularly reduced.