Enantioselective Additions of Aryltitanium Tris(isopropoxide) to Ketones: Structure of [(i‐PrO)2Ti{μ‐(S)‐BINOLate}(μ‐O‐i‐Pr)TiPh(O‐i‐Pr)2], Study of Mechanistic and Stereochemical Insights

Aryl addition reactions of ArTi(O‐i‐Pr)₃ to aromatic, heteroaromatic, or α,β‐unsaturated ketones are described, producing tertiary alcohols in good to excellent enantioselectivities of up to 97% ee. The structure of the dititanium complex [(i‐PrO)₂Ti{μ‐(S)‐BINOLate}(μ‐O‐i‐Pr)TiPh(O‐i‐Pr)₂] [(S)‐ 4 ] that simultaneously bears a chiral directing ligand and a nucleophile is reported. Complex (S)‐ 4 possesses a pocket structure and has been illustrated as the key active species for addition reactions of both aldehydes and ketones. Mechanistic and stereochemical insights concerning addition reactions of organometallic reagents to organic carbonyls are rationalized based on the pocket structure and pocket size of (S)‐ 4 .     

Aerodynamique de l'ecoulement vertical de suspensions concentrees gaz-solides—I. Regimes d'ecoulement et stabilite aerodynamique

In the course of a more general study on vertical pneumatic transport catalytic reactors we have been led to investigate more particularly the aerodynamics of concentrated gas-solid suspensions at low velocities. Here we describe the various flow regimes encountered under these conditions. The prediction of choking flowrates and concentrations can be made from a mathematical model based on a single stability criterium. This model is a good agreement with our experimental results and the data of other authors.     

Redox kinetics of benzene oxidation to maleic anhydride

Steady state kinetics of the oxidation reaction have been determined with the help of a gradientless semi-differential, fixed-bed reactor. The Mars and van Krevelen phenomenological model satisfactorily correlates the experimental data but a modification of the Langmuir-Hinshelwood model taking into account partial coverage of the catalyst surface with reaction intermediates is preferred. Transient kinetics have been studied with a new automated periodic-pulse reactor, directly connected to a gas chromatograph. The response of a catalyst (essentially V₂O₅–MoO₃) to reduction and oxidation has been investigated. The rate of bulk (lattice) oxygen utilization as well as the degree of carbon coverage are estimated by this technique. Selectivity is dependent on the oxidation state of the catalyst: high partial pressure of either benzene or oxyen and high temperatures are detrimental to selectivity.     

Effects of poly(vinyl acetate) and poly(vinyl chloride‐ co‐vinyl acetate) low‐profile additives on properties of cured unsaturated polyester resins. I. Volume shrinkage characteristics and internal pigmentability

Three series of self‐synthesized poly(vinyl acetate)‐based low‐profile additives (LPAs) with different chemical structures and molecular weights, including poly(vinyl acetate), poly(vinyl chloride‐co‐vinyl acetate), and poly(vinyl chloride‐co‐vinyl acetate‐co‐maleic anhydride), were studied. Their effects on the volume shrinkage characteristics and internal pigmentability for low‐shrink unsaturated polyester (UP) resins during cure were investigated. The experimental results were examined with an integrated approach involving measurements of the static phase characteristics of the ternary styrene/UP/LPA system, the reaction kinetics, the cured sample morphology, and microvoid formation by using differential scanning calorimetry, scanning electron microscopy, optical microscopy, and image analysis. Based on the Takayanagi mechanical model, factors leading to both good volume shrinkage control and acceptable internal pigmentability for the molded parts were explored. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3336–3346, 2003     

Applying forming simulation to process and tooling designs for minimizing springback in split dowel manufacturing

In this study, FEA simulations were conducted to analyze the forming and springback of a split dowel forming process. Through 96 simulations, the best dimensional quality product from the current production tooling was obtained. However, it still cannot meet the customer’s geometrical requirement, so a metal finish process (secondary operation) is required. In order to minimize manufacturing cost and time, the secondary operation is not desired. Therefore, a new forming process and die design were developed through many iterative FEA simulations. This new design adds a short coin bead on the seam line area of the split dowel. It has been found that the springback amount is almost eliminated and the product quality exceeds the customer’s geometry requirement. Through this real industry case study, it is shown that FEA simulation can be used to not only optimize the current process but also design a new process and tooling.     

Performance analysis of Finite-User slotted aloha in wireless networks with multiple packet reception and random traffic

In this paper, we propose an analytical approach for evaluating the performance of finite-user slotted Aloha in wireless networks with multiple packet reception and random traffic. We derive the exact values of the throughput, the average system size, the packet blocking probability, and the average system delay. Our analysis is based on probability theory. We show that our numerical results are identical to simulation results.     

Film cooling performance and heat transfer over an inclined film-cooled surface at different convergent angles with respect to highly turbulent mainstream

Experiments have been performed to study and obtain the adiabatic-wall film cooling effectiveness and the heat transfer over a film-cooled surface that is made inclined at various angles with respect to a highly turbulent flow. The film-cooled air is injected from a tangential slot. The normal temperature distributions were measured to infer the flow structure and the rate of mixing of film jet with the freestream. The freestream turbulence intensity is controlled to range from 1.0% to 26.4%, the inclination or the convergent angle of the film-cooled surface ranges from 0° to 20°, the blowing parameter from 0.5 to 2.0. It is found that the mixing of the film jet with the freestream is significantly enhanced by both the freestream turbulence intensity and the convergent angle of the film-cooled surface, which leads to the decrease in the film cooling effectiveness and the increase in the heat transfer when the inclination angle of the film-cooled surface is not large. This is attributed to the two competition mechanisms of impinging effect and the stabilization due to acceleration of the mainstream. The normal temperature distribution at several locations along the flow direction is also measured and used to infer the flow structure of the mixing of film jet with the mainstream. More detailed discussion is presented. Correlations for both the film cooling effectiveness and the heat transfer under the film-cooled surface have been very successful and are provided.     

Cutter-path generation using multiple cutting-tool sizes for 2-1/2D pocket machining

Existing commercial CAD/CAM systems allow the user to generate the cutter-path for machining a 2-1/2D pocket by using only a single cutting-tool size. Therefore, to avoid potential problems, such as gouging and unmachined areas, the user tends to choose the size of the cutting-tool in a conservative manner. This can result in longer processing time and higher production cost than those that can be achieved by using multiple cutting-tool sizes to machine a given pocket. The key to cutter-path generation using multiple cutting-tool sizes lies in having an efficient mechanism for representing the material volumes that can be removed by a specified cutting-tool size and the unmachined material volumes that will remain after its use. In this paper, we develop a novel concept called the Voronoi mountain and describe its application to cutter-path generation using multiple cutting-tool sizes. The theoretical significance of this approach stems from its ability to: (i) to create a Voronoi mountain representation of unmachined material volumes without having to construct the corresponding Voronoi diagram; and (ii) to accommodate generalized pocket geometries.     

Efficacy trial of a brief cognitive–behavioral depression prevention program for high-risk adolescents: Effects at 1- and 2-year follow-up.

Objective: To evaluate the effects of a brief group cognitive–behavioral (CB) depression prevention program for high-risk adolescents with elevated depressive symptoms at 1- and 2-year follow-up. Method: In this indicated prevention trial, 341 at-risk youths were randomized to a group CB intervention, group supportive expressive intervention, CB bibliotherapy, or educational brochure control condition. Results: Significantly greater reductions in depressive symptoms were shown by group CB participants relative to brochure control participants by 1-year follow-up and bibliotherapy participants by 1- and 2-year follow-up but not relative to supportive expressive participants. Supportive expressive participants showed greater symptom reduction than CB bibliotherapy participants did at 2-year follow-up. Risk for onset of major or minor depression over the 2-year follow-up was significantly lower for group CB participants (14%; odds ratio = 2.2) and CB bibliotherapy participants (3%; odds ratio = 8.1) than for brochure controls (23%). Conclusions: Results indicate that this group CB intervention reduces initial symptoms and risk for future depressive episodes, although both supportive expressive therapy and CB bibliotherapy also produce intervention effects that persist long term. Indeed, CB bibliotherapy emerged as the least expensive method of reducing risk for future episodes of depression. (PsycINFO Database Record (c) 2010 APA, all rights reserved)