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.     

Strong formulations for mixed integer programs: valid inequalities and extended formulations

 We examine progress over the last fifteen years in finding strong valid inequalities and tight extended formulations for simple mixed integer sets lying both on the ``easy' and ``hard' sides of the complexity frontier. Most progress has been made in studying sets arising from knapsack and single node flow sets, and a variety of sets motivated by different lot-sizing models. We conclude by citing briefly some of the more intriguing new avenues of research. Received: January 15, 2003 / Accepted: April 10, 2003 Published online: May 28, 2003 Key words. mixed integer programming – strong valid inequalities – convex hull – extended formulations – single node flow sets – lot-sizing This paper presents research results of the Belgian Program on Interuniversity Poles of Attraction initiated by the Belgian State, Prime Minister's Office, Science Policy Programming. The scientific responsibility is assumed by the authors. Research carried out with financial support of the project TMR-DONET nr. ERB FMRX–CT98–0202 of the European Union.     

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.     

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.     

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     

New theoretical insight into the interactions and properties of formic acid: development of a quantum-based pair potential for formic acid

We performed ab initio quantum-chemical studies for the development of intra- and intermolecular interaction potentials for formic acid for use in molecular-dynamics simulations of formic acid molecular crystal. The formic acid structures considered in the ab initio studies include both the cis and trans monomers which are the conformers that have been postulated as part of chains constituting liquid and crystal phases under extreme conditions. Although the cis to trans transformation is not energetically favored, the trans isomer was found as a component of stable gas-phase species. Our decomposition scheme for the interaction energy indicates that the hydrogen-bonded complexes are dominated by the Hartree-Fock forces while parallel clusters are stabilized by the electron correlation energy. The calculated three-body and higher interactions are found to be negligible, thus rationalizing the development of an atom-atom pair potential for formic acid based on high-level ab initio calculations of small formic acid clusters. Here we present an atom-atom pair potential that includes both intra- and inter molecular degrees of freedom for formic acid. The newly developed pair potential is used to examine formic acid in the condensed phase via molecular-dynamics simulations. The isothermal compression under hydrostatic pressure obtained from molecular-dynamics simulations is in good agreement with experiment. Further, the calculated equilibrium melting temperature is found to be in good agreement with experiment.     

A theoretical investigation of the preferred conformations of glutathione and its constituent amino acid residues

The preferred conformations of the tripeptide glutathione have been investigated by performing quantum mechanical calculations using the PCILO method. A series of model compounds representing fragments of the tripeptide has been studied as well as the complete molecule. The results are compared with the available experimental data.