Self-assembled host-guest nanostructures on gold electrodes for thiodianiline determination

Self-assembled monolayers of thiolated β-cyclodextrins on a gold electrode have been developed for the determination of thiodianiline. Pentanethiol was employed to fill the empty space between the β-cyclodextrins on the surface. The formation of a 1:2 inclusion complex between thiodianiline and β-cyclodextrin was studied by electrochemistry. The parameters affecting the modification of the electrode and the determination of thiodianiline by square wave voltammetry were optimized. The limits of detection and determination are 190 and 205 μg?L^?1, respectively. The accuracy, in terms of relative error values, is <7%. The precision, in terms of RSD (for n?=?5), is <5%. The method was applied to the determination of thiodianiline in real wastewater samples with RSD values of <11% and an average recovery of 98% for all the spiking levels assayed.     

Dearomatizing anionic cyclization of N-methyl-N-benzyldi(1-naphthyl)phosphinamide: a route for access to a new class of functionalized tricyclic azaphospholes with antitumor properties

The dearomatizing anionic cyclization of N-alkyl-N-benzyldi(1-naphthyl)phosphinamide 1d followed by trapping with a series of carbonyl reagents and α,β-unsaturated ketones under optimized conditions provided new tetrahydro-1H-naphtho[1,2-c][1,2]-azaphosphole 1-oxides from moderate to high yields and diastereoselectivities. In addition, two doubly dearomatized compounds as a result of double dearomatization on the two naphthalene rings of 1d have been isolated at first time. Three functionalized azaphospholes have been evaluated on three different human tumor cell lines showing growth inhibition factors (GI₅₀) at a micromolar scale. One of these heterocycles has also shown cytostatic properties.     

Das Vorhersagerisiko der Sterblichkeitsentwicklung – Kann es durch eine geeignete Portfoliozusammensetzung minimiert werden?

Annuities as well as term insurance create risks for the insurance companies due to changes in mortality/longevity – especially in low-interest phases. For the past decades an increase in life expectancy was observed. In this article, we examine whether an insurance company can minimise the longevity risk by means of an appropriate composition of its portfolio. We use stochastic interest rates and mortality trends. For annuities and term insurance different mortality trends are used. Based on an example we show the impact of the portfolio composition on the longevity risk. The results prove that a deliberate portfolio composition can significantly reduce the longevity risk for the insurance company.     

A new approach for solving linear bilevel problems using genetic algorithms

Bilevel programming involves two optimization problems where the constraint region of the first level problem is implicitly determined by another optimization problem. This paper develops a genetic algorithm for the linear bilevel problem in which both objective functions are linear and the common constraint region is a polyhedron. Taking into account the existence of an extreme point of the polyhedron which solves the problem, the algorithm aims to combine classical extreme point enumeration techniques with genetic search methods by associating chromosomes with extreme points of the polyhedron. The numerical results show the efficiency of the proposed algorithm. In addition, this genetic algorithm can also be used for solving quasiconcave bilevel problems provided that the second level objective function is linear.     

From central to helical chirality: synthesis of P and M enantiomers of [5]helicenequinones and bisquinones from (SS)-2-(p-tolylsulfinyl)- 1,4-benzoquinone

The reaction of 1,4-divinyl-1,3-cyclohexadiene, 5,8-dimethoxy- or tert-butyldimethylsilyloxy-3-vinyl-1,2-dihydrophenanthrene or 6-vinyl-7,8-dihydro-1,4-phenanthrenequinone with an excess of enantiopure (SS)-2-(p-tolylsulfinyl)-1,4-benzoquinone (2) led to the direct formation of enantioenriched dihydro[5]helicenequinones or bisquinones (50-->98 % ee). A domino Diels-Alder cycloaddition/sulfoxide elimination/partial aromatization process occurs, being the absolute configuration of the final helicene defined in the aromatization step. Both M and P helimers are accessible through a stepwise enantiodivergent process if the pentacyclic dihydroaromatic intermediate resulting in the two first steps is aromatized in the presence of (+/-)-2, DDQ, CAN or DBU.     

Bayesian inference in Markovian queues

This paper is concerned with the Bayesian analysis of general queues with Poisson input and exponential service times. Joint posterior distribution of the arrival rate and the individual service rate is obtained from a sample consisting inn observations of the interarrival process andm complete service times. Posterior distribution of traffic intensity inM/M/c is also obtained and the statistical analysis of the ergodic condition from a decision point of view is discussed.