Rational Development of Remote C−H Functionalization of Biphenyl: Experimental and Computational Studies

A simple and efficient nitrile-directed meta-C−H olefination, acetoxylation, and iodination of biaryl compounds is reported. Compared to the previous approach of installing a complex U-shaped template to achieve a molecular U-turn and assemble the large-sized cyclophane transition state for the remote C−H activation, a synthetically useful phenyl nitrile functional group could also direct remote meta-C−H activation. This reaction provides a useful method for the modification of biaryl compounds because the nitrile group can be readily converted to amines, acids, amides, or other heterocycles. Notably, the remote meta-selectivity of biphenylnitriles could not be expected from previous results with a macrocyclophane nitrile template. DFT computational studies show that a ligand-containing Pd–Ag heterodimeric transition state (TS) favors the desired remote meta-selectivity. Control experiments demonstrate the directing effect of the nitrile group and exclude the possibility of non-directed meta-C−H activation. Substituted 2-pyridone ligands were found to be key in assisting the cleavage of the meta-C−H bond in the concerted metalation–deprotonation (CMD) process.     

流动系统中鲁米诺电生化学发光(ECL)系统研究初探

本文描述了一个新的鲁米诺电生化学发光流动系统.通过微铂电极流动池,H2O2被还原为OH-以维持鲁米诺化学发光所要求的pH条件.本文对鲁米诺化学发光机理进行了初步探讨,并详细研究了ECL的最佳条件,该系统明显降低了反应噪声,优于混合反应系统,可作为液相色谱间接测定检测器.     

Subgame Consistent Cooperative Solutions in Stochastic Differential Games

Subgame consistency is a fundamental element in the solution of cooperative stochastic differential games. In particular, it ensures that: (i) the extension of the solution policy to a later starting time and to any possible state brought about by the prior optimal behavior of the players would remain optimal; (ii) all players do not have incentive to deviate from the initial plan. In this paper, we develop a mechanism for the derivation of the payoff distribution procedures of subgame consistent solutions in stochastic differential games with transferable payoffs. The payoff distribution procedure of the subgame consistent solution can be identified analytically under different optimality principles. Demonstration of the use of the technique for specific optimality principles is shown with an explicitly solvable game. For the first time, analytically tractable solutions of cooperative stochastic differential games with subgame consistency are derived.     

Supporting Preservice Teachers' Understanding of Place Value and Multidigit Arithmetic

This article provides an analysis of a teaching experiment conducted in the context of teacher education designed to support preservice teachers' understandings of place value and multidigit addition and subtraction. The experiment addresses the following research question: Can the results from research conducted in elementary mathematics classrooms guide preservice elementary teachers' development of conceptual understanding of the same concepts? In both cases, the students (e.g., elementary students and preservice teachers) participated in activities from an instructional sequence designed to support conceptual understanding of both place value and multidigit addition and subtraction. Analyses of the episodes from the teaching experiment document the learning of the preservice teachers and how that learning was supported by initial conjectures grounded in the research on elementary students' ways of reasoning.     

Optimization for pattern classification using biased random search techniques

We demonstrate how optimization problems arise in the field of pattern classification, in particular in using piecewise-linear classification and classification based on an optimal linear separator. We motivate the need in this area for a general purpose optimization approach. We discuss ALOPEX, a biased random search approach, from the point of view of this need. While ALOPEX itself failed to fulfil our need, a newly-introduced generalization of it (iterated ALOPEX) was found to be appropriate for the optimization problems of our particular concern. We conclude the paper with a brief critical evaluation of this approach as compared to our original aims.     

The effect of solvent upon molecularly thin rotaxane film formation

We have investigated variations in molecularly thin rotaxane films deposited by solvent evaporation, using atomic force microscopy (AFM). Small changes in rotaxane structure result in significant differences in film morphology. The addition of exo-pyridyl moietes to the rotaxane macrocycle results in uniform domains having orientations corresponding to the underlying substrate lattice, while a larger, less symmetric molecule results in a greater lattice mismatch and smaller domain sizes. We have measured differences in film heights both as a function of the solvent of deposition and as a function of surface coverage of rotaxanes. Based on these observations we describe how the use of solvents with higher hydrogen-bond basicity results in films which are more likely to favour sub-molecular motion.     

Pd (II)‐catalyzed vinyl addition polymerization of novel functionalized norbornene bearing dimethyl carboxylate groups

Three novel functionalized polynorbornenes (PNB) with pendant dimethyl carboxylate group (carboxylates—acetate, propionate, and butyrate) are synthesized as a vinyl‐type with a palladium (II) catalyst in high yield. The effects of size of substitutents, molar ratio of monomer to catalyst, solvent polarity, reaction time, and temperature on the polymerization of exo‐norbornene dimethyl propionate were systematically investigated. The low molar ratio and temperature, as well as high polarity of solvent, and long reaction time, are favorable for the enhancement of the monomer conversion, especially, the solvent have an obvious effect on the catalyst activity. The resulting poly(cis‐norbornene‐exo‐2,3‐dimethyl carboxylates) (PNB‐dimethyl carboxylates) show good solubility in common organic solvent and high thermal stability up to 360 °C. The glass transition temperature was detected by DMA at 331, 324, and 318 °C for acetate, propionate, and butyrate, respectively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3391–3399, 2007