Beyond Ugi and Passerini reactions: multicomponent approaches based on isocyanides and alkynes as an efficient tool for diversity oriented synthesis

The reaction of isocyanides with electron deficient alkynes has been first reported in 1969, about ten years after the first reports on the famous Ugi four component reaction. However it took about thirty years to realise that the zwitterionic intermediate originating from interaction of the two species could be trapped by a third component, thus giving the start to a novel class of isocyanide-based multicomponent reactions. From that first report dated 1996 there has been an ongrowing interest that has produced, so far, about 150 distinct scientific papers. This review is aimed at rationalising and cathegorising these reports and at offering an overview of all the possible applications of this novel methodology.     

NSGA-II-RJG applied to multi-objective optimization of polymeric nanoparticles synthesis with silicone surfactants

Polydimethylsiloxane nanoparticles were obtained by nanoprecipitation, using a siloxane surfactant as stabilizer. Two neural networks and a genetic algorithm were used to optimize this process, by minimizing the particle diameter and the polydispersity, finding in this way the optimum values for surfactant and polymer concentrations, and storage temperature. In order to improve the performance of the non-dominated sorting genetic algorithm, NSGA-II, a genetic operator was introduced in this study — the transposition operator — “real jumping genes”, resulting NSGA-II-RJG. It was implemented in original software and was applied to the multi-objective optimization of the polymeric nanoparticles synthesis with silicone surfactants. The multi-objective function of the algorithm included two fitness functions. One fitness function was calculated with a neural network modelling the variation of the particle diameter on the surfactant concentration, polymer concentration, and storage temperature, and the other was computed by a neural network modelling the dependence of polydispersity index on surfactant and polymer concentrations. The performance of the software program that implemented NSGA-II-RJG was highlighted by comparing it with the software implementation of NSGA-II. The results obtained from simulations showed that NSGA-II-RJG is able to find non-dominated solutions with a greater diversity and a faster convergence time than NSGA-II.      

Computational experience with a bundle approach for semidefinite cutting plane relaxations of Max-Cut and Equipartition

We propose a dynamic version of the bundle method to get approximate solutions to semidefinite programs with a nearly arbitrary number of linear inequalities. Our approach is based on Lagrangian duality, where the inequalities are dualized, and only a basic set of constraints is maintained explicitly. This leads to function evaluations requiring to solve a relatively simple semidefinite program. Our approach provides accurate solutions to semidefinite relaxations of the Max-Cut and the Equipartition problem, which are not achievable by direct approaches based only on interior-point methods. Received: April, 2004 The last author gratefully acknowledges the support from the Austrian Science Foundation FWF Project P12660-MAT.     

Enzymatic hydrolysis of steam-exploded and ethanol organosolv-pretreated douglas-fir by novel and commercial fungal cellulases

Softwood residues are the most abundant feedstock available for bioconversion in many northern countries. However, the high costs for delignification and enzymatic hydrolysis currently deter commercialization of softwood bioconversion processes. This study evaluates the abilities of two novel fungal preparations (MSUBC1 and MSUBC2) and two commercial cellulase preparations (TR1 and TR2) to hydrolyze cellulose in Douglas-fir pretreated by steam explosion or ethanol organosolv process. MSUBC1 showed significantly better performance than the other preparations on both lignocellulosic substrates. In particular, MSUBC1 achieved >76% cellulose conversion for hydrolysis of steam-exploded Douglas-fir (～44% lignin) after 72 h at low enzyme loading (10 filter paper units/g of cellulose) and without β-glucosidase supplementation.     

Spectroscopic study of a representative polar cap of buckminsterfullerene: Cyclopentacorannulene

The spectroscopic properties of corannulene and cyclopentacorannulene are examined by use of absorption and steady-state fluorescence measurements. A red shift in the emission maxima of cyclopentacorannulene is noted with respect to the emission maxima in the corannulene spectrum. Similar differences in the absorption spectra of both molecules are also observed. Reasons for the dissimilarities in the absorption and emission spectra of these molecules are discussed. The fluorescence quantum yields and lifetimes of the molecules measured in organic solvents are reported. The fluorescence quantum yield and lifetime of cyclopentacorannulene are lower than those of corannulene. This difference is attributed to the highly strained and nonplanar structure of cyclopentacorannulene. The effectiveness of nitromethane as a quencher of corannulene and cyclopentacorannulene fluorescence is examined. In contrast to previously reported results, the fluorescence of these molecules is quenched by nitromethane. Fluorescence quenching of the molecules has been attributed to complex formation in the ground state, i.e., static quenching.     

Organic conductors based on 2,5-diamino-3,4-dicyanothiophene and diaminomaleonitrile and their transformation to new phthalocyanine analogues

New phihalocyanine analogues were prepared based on 2,5-diamond-3,4-dicyanothiophene and diaminomaleo-nitrile.Department of Organic Chemistry, Slovak Technical University, Bratislava, Slovakia. Institute für Festkörperphysik der Universität Wien, Wien, Austria. Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1409–1411, October, 1995. Original article submitted September 24, 1995.