Synergy,Compatibility, and Innovation: Merging Lewis Acids with Stereoselective Enamine Catalysis

In recent years there has been an accelerated rate of development in the field of organocatalysis, with asymmetric organocatalysis now reaching full maturity. The invention of new organocatalytic reactions and the exploration of new concepts now appear in tandem with the application of organocatalytic techniques in the synthesis of natural products and active pharmaceutical ingredients (APIs). After a “golden rush” in organocatalysis, researchers are now starting to combine different methods, thereby taking advantage of the significant benefits of synergy. Metals are used in combination with organocatalytic processes, thus reaching complexity that is found in nature, where enzymes take advantage of the presence of certain metals to increase the arsenal of organic transformations available. In this Focus review, we illustrate the possibility of a “happy marriage” between Lewis acids and organocatalytic stereoselective processes. Questions have been raised about the combination of Lewis acids and organocatalysis owing to the presence of water and/or strong bases in these processes. Some Lewis acids have been shown to be compatible with organocatalysis and concepts relating to their use will be illustrated herein. To summarize the fruitful use of Lewis acids in stereoselective organocatalytic processes, we will draw attention to the advantages and selectivity achieved using this method.     

Numerical analysis of mixed convection in three‐dimensional rectangular channel with flush‐mounted heat sources based on field synergy principle

In this paper the fluid flow and heat transfer characteristics of mixed convection in three‐dimensional rectangular channel with four heat sources are investigated numerically. The SIMPLEC algorithm is applied to deal with the coupling between pressure and velocity, and a new high‐order stability‐guaranteed second‐order difference (SGSD) scheme is adopted to discretize the convection term. The influence of four parameters is studied: Richardson number, heat source distribution, channel height and inclination angle. The numerical results are analysed from the viewpoint of the field synergy principle, which says that the enhanced convective heat transfer is related not only to the velocity field and temperature field, but also to the synergy between them. It is found that the effects of the four parameters on the thermal performance can all be explained with the field synergy principle. To obtain better electronic cooling, the synergy between the velocity and temperature gradient should be increased when other conditions are unchanged. Copyright © 2006 John Wiley & Sons, Ltd.     

磁热场协同作用下的传热传质强化

通过三维非稳态动量和能量方程的模拟,对圆管通道内空气的磁热风作用机理进行了分析。得出了无量纲长径比为 20、30、62和100,带电线圈和管道的直径比从2到200时磁场密度的梯度的影响规律。磁场与温度场的协同作用改变了速度和温度边界层的分布,存在最优条件下的强化传热、传质效果。     

Synergy between manipulative and digital artefacts: a teaching experiment on axial symmetry at primary school

This paper presents a study aimed at investigating the didactic potentiality of the combined use of two different kinds of artefacts for the purpose of constructing and conceptualizing mathematical meanings related to the notion of axial symmetry. In our view, the process of meanings construction can be fostered by the use of adequate artefacts, but it requires a teaching/learning model, which explicitly takes care of the evolution of meanings, from those personal, emerging through the activities, to the mathematical ones, aims of the teaching intervention. The main hypothesis of this study is that a potential synergy may occur between the use of different artefacts, synergy that can foster the integration of different and complementary meanings providing a rich support to the development of the expected mathematical meaning. The Theory of Semiotic Mediation offers the theoretical framework suitable to design the teaching sequence and to analyze the collected data. Specifically, the construct of semiotic potential provides the tool for describing the potentialities of the two artefacts, while that of didactic cycle offers a model for the organization of the different activities. The paper reports on a teaching sequence and its implementation in a teaching experiment, involving pupils at fourth grade level. We describe them, within the chosen theoretical framework, and provide the analysis of key episodes of the teaching sequence. We show evidence supporting our main hypothesis about the combined use of an artefact that can be manipulated (paper and pin), and a digital artefact (Dynamic Geometry Environment) in the development of the notion of axial symmetry and its properties: the combined, intentional and controlled use of the two artefacts may develop a synergy, so that each activity enhances the potential of the other.     

强化换热通道中扰流元场协同优化研究

对一种场协同式周期性强化换热通道进行了数值模拟研究,考察了折流翅片不同角度、不同间距对通道换热特性的影响。计算结果表明,翅片倾角增大或间距缩小均有利于换热强化。强化效果随Re数的增大而愈加显著。     

行业结构环境的序参量分析方法研究

行业结构环境分析是发现和掌握行业运行规律与发展状况的必经之路,也是在企业战略管理中的重要组成部分,其结果直接影响着企业战略决策与实施。针对企业战略管理的新价值理念,本文在协同学与竞优理论的基础上,通过对行业内群体结构特性与企业行为的重新考察,建立了行业结构环境分析的一种新方法即序参量分析方法与其应用范例。本文的研究结果,如行业内多层结构、企业群组定位及分布特性、行业基本发展模式、标杆与协同伙伴、企业群组或群组内企业构成与绩效之间的关系等都可为实现符合现代产业发展环境的企业战略管理提供方向性辅助与技术支持。     

丙烷氧化脱氢VMgO催化剂双相协同催化作用

研究了以重质氧化镁载体浸渍偏钒酸铵水溶液制备的５－８２ＶＭｇＯ系列催化剂在５００℃下的丙烷氧化脱氢反应。该系列催化剂的活性和选择性比柠檬酸盐法制备的纯钒酸镁和文献报道打应催化剂好。     

Viscous Synergy of Pure Monoalcohol Mixtures in Water and Its Relation to Concentration

Pure or aqueous alcohols are the solvents most widely used in industry, including in the manufacture of pharmaceuticals and cosmetic products. However, water–alcohol mixtures generate hydrogen-bonded molecular associations that lead to volume contraction and an increase in viscosity greater than that expected in the absence of any interaction between the components of the mixture. This phenomenon is referred to as viscous synergy. The present study investigates viscous synergy in monoalcohol systems containing up to five carbon atoms, since beyond hexanol all alcohols are practically insoluble in water. In all cases, determinations were made of the proportions of water and alcohol for which maximum viscosity is observed, together with the corresponding synergy index. An enhancement index has likewise been introduced, defined as: E = _max/₀), where _max is the maximum viscosity reached in the water–alcohol mixture, and ₀ is the viscosity of the pure alcohol.     

Heterodinuclear Mg(II)M(II) (M=Cr,Mn, Fe,Co, Ni,Cu and Zn) Complexes for the Ring Opening Copolymerization of Carbon Dioxide/Epoxide and Anhydride/Epoxide

The catalysed ring opening copolymerizations (ROCOP) of carbon dioxide/epoxide or anhydride/epoxide are controlled polymerizations that access useful polycarbonates and polyesters. Here, a systematic investigation of a series of heterodinuclear Mg(II)M(II) complexes reveals which metal combinations are most effective. The complexes combine different first row transition metals (M(II)) from Cr(II) to Zn(II), with Mg(II); all complexes are coordinated by the same macrocyclic ancillary ligand and by two acetate co-ligands. The complex syntheses and characterization data, as well as the polymerization data, for both carbon dioxide/cyclohexene oxide (CHO) and endo-norbornene anhydride (NA)/cyclohexene oxide, are reported. The fastest catalyst for both polymerizations is Mg(II)Co(II) which shows propagation rate constants (k_p) of 34.7 mM⁻¹ s⁻¹ (CO₂) and 75.3 mM⁻¹ s⁻¹ (NA) (100 °C). The Mg(II)Fe(II) catalyst also shows excellent performances with equivalent rates for CO₂/CHO ROCOP (k_p=34.7 mM⁻¹ s⁻¹) and may be preferable in terms of metallic abundance, low cost and low toxicity. Polymerization kinetics analyses reveal that the two lead catalysts show overall second order rate laws, with zeroth order dependencies in CO₂ or anhydride concentrations and first order dependencies in both catalyst and epoxide concentrations. Compared to the homodinuclear Mg(II)Mg(II) complex, nearly all the transition metal heterodinuclear complexes show synergic rate enhancements whilst maintaining high selectivity and polymerization control. These findings are relevant to the future design and optimization of copolymerization catalysts and should stimulate broader investigations of synergic heterodinuclear main group/transition metal catalysts.