Studies on the oxidation of enamines with molecular oxygen. I. Oxidation of Some Piperidino Alkenes

In the autoxidation of 1-piperidinocyclohex-1-ene ( 1 ), 1-piperidinobut-1-ene ( 2 ), 3-piperidinopent-2-ene ( 3 ), and 1-piperidino-2-methyl-prop-1-ene( 4 ) only products of an oxidative attack at the CC-double bond are formed. Both α-aminoketones, the products of the rearrangement of primarily formed epoxides, and products of the oxidative session of the CC double bond are obtained. As a side reaction some hydrolysis of the starting enamines takes place. This hydrolysis proves that some water must be formed during the enamine oxidation.     

Validation and application of an LC-MS/MS method for the determination of cyclic oligomers originating from polyamide 6 and polyamide 66 in food simulant

Polyamides (PAs) are used in the production of various food contact materials (FCMs) and articles such as kitchen utensils and packaging material. Cyclic oligomers have been identified as potential migrants from PA. This study describes the development, validation and application of a multi-oligomer analytical method based on LC-ESI-MS/MS for the identification and quantification of eight cyclic oligomers of PA 6 and four PA 66 migrating from FCMs into food simulant B (3% acetic acid) and beverages. It was proved that doubly charged precursor ions of the cyclic PA 6 and PA 66 oligomers above a mass of 500 Da are formed during the ionisation process of the electrospray technique used. Direct injection of a diluted food simulant into the LC-ESI-MS/MS system after migration makes the validated method a valuable tool for investigating migration of cyclic PA oligomers. The validation results demonstrate that the multi-oligomer method is applicable for the analysis of cyclic PA 6 and PA 66 oligomers in food simulant B. For all investigated cyclic PA oligomers, detection limits were in the range of 0.1–1.1 µg/l. Linearity (r² ≥ 0.99), trueness values between 91% and 122%, and intra-day (RSD_r < 10%) and inter-day precision (RSD_R < 19%) were determined and satisfied validation criteria set out by the European Reference Laboratory for FCMs. The method was extended to tap water and tea. Finally, the multi-oligomer method was successfully applied to determine cyclic PA oligomers in migration solutions originating from different PA FCMs. In all migration solutions, concentrations of cyclic PA oligomers were determined above the LOQ. A preliminary risk assessment based on in silico tools was performed. The results demonstrate the urgent need for toxicological data that would facilitate the evaluation of the health risk of cyclic PA oligomers.     

Influence of a joining helix on the BLUF domain of the YcgF photoreceptor from Escherichia coli

BLUF-domain-comprising photoreceptors sense blue light by utilizing FAD as a chromophore. The ycgF gene product of Escherichia coli is composed of a N-terminal BLUF domain and a C-terminal EAL domain, with the latter postulated to catalyze c-di-GMP hydrolysis. The linkage between these two domains involves a predominantly helical segment. Its role on the function of the YcgF photoreceptor domain was examined by characterizing BLUF domains with and without this segment and reconstituting them with either FAD, FMN or riboflavin. The stability of the light-adapted state of the YcgF BLUF domain depends on the presence of this joining, helical segment and the adenosine diphosphate moiety of FAD. In contrast to other BLUF domains, two-dimensional (1)H,(15)N and one-dimensional (1)H NMR spectra of isotope-labeled YcgF-(1-137) revealed large conformational changes during reversion from the light- to the dark-adapted state. Based on these results the function of the joining helix in YcgF during signal transfer and the role of the BLUF domain in regulating c-di-GMP levels is discussed.     

Distinguishing anxiety and depression: Reexamination of the reconstructed Hamilton scales.

The discriminant validities of the original and the reconstructed Hamilton anxiety and depression scales (J. H. Riskind et al, 1987) were compared in patients who had principal Diagnostic and Statistical Manual of Mental Disorders-III—Revised (DSM-III—R) anxiety disorders with or without 1 or more comorbid mood disorders. The reconstructed anxiety and depression scales had better discriminant validity (scale intercorrelation?=?.61) than the original scales did (r?=?.78). However, the reconstructed scales shared considerable variance (about 37%), which was significantly higher than the shared variance (about 2%) reported by Riskind et al. Discriminant analyses showed that the reconstructed scales did not distinguish anxiety patients with comorbid mood disorders from those without comorbid mood disorders better than the original scales did. However, the reconstructed scales eliminate item overlap, an obvious source of artifactual correlations between scores on the Hamilton anxiety and depression scales. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

A computational approach to modeling commodity markets

We build an agent based computational framework to study large commodity markets. A detailed representation of the consumers, producers and the market is used to study the micro level behavior of the market and its participants. The user can control players’ preferences, their strategies, assumptions of the model, its initial conditions, market elements and trading mechanisms. The first part of the paper describes the computational framework and its three main modules. The later part describes a case study that examines the decentralized market in detail, specifically the computational options available for matching the buyers and suppliers in a synthetic market. The study illustrates the sensitivity of the outcome of various economic variables, such as clearing price, quantity, profits and social welfare, to different matching schemes in a bilateral computational setting. Based on seven different matching orders for the buyers and suppliers, our study shows that the results can vary dramatically for different pairing orders.     

Development of sex-differentiated preferences during late childhood and adolescence.

Examined factors influencing sex-differentiated responses to selected interests and interpersonal traits by young people in 3 age groups: 516 in late childhood (Grades 4–6), 398 in early adolescence (Grades 7–9), and 337 in late adolescence (Grades 10–12). There was limited evidence for same-sex bias during late childhood, varying by sex and race in its pervasiveness or clarity. Interpersonal traits were not generally sex stereotyped. Several interests were sex stereotyped during adolescence, but not those most directly related to academic learning. In general, interests were more strongly sex stereotyped by boys than by girls. Greater cognitive maturity generally attenuated sex stereotyping of interests. Certain developmental trends differed by sex and/or by race, and socioeconomic background (parents" education) influenced developmental trends among Blacks but not among Whites. (37 ref) (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Modifying the adsorption behavior of polyamidoamine dendrimers at silica surfaces investigated by total internal reflection fluorescence correlation spectroscopy

Polyamidoamine (PAMAM) dendrimers were modified and tested for use as solution-phase diffusion probes in silica nanostructures. In order for the successful application of dendrimers as solution-phase probes, their interactions with silica surfaces must be understood and controlled, so that the motion of the probe is not influenced by adsorption. Adsorption/desorption kinetics of PAMAM dendrimers and their diffusion in solution near silica surfaces were investigated with total internal reflection fluorescence correlation spectroscopy (TIR-FCS). Dendrimers of generations 3, 5, and 7 were dye-labeled with carboxyrhodamine 6G. Because PAMAM dendrimers are positively charged in solution (having primary amines as end groups), significant adsorption of these molecules to the negatively charged silica surface was observed. Adsorption/desorption rates and the equilibrium constant for adsorption were determined by fitting the autocorrelation functions to a kinetic model. The desorption rate decreases and the absorption equilibrium constant increases with higher dendrimer generation. To reduce the adsorption of these probes to silica surfaces, the labeled dendrimers were reacted with succinic anhydride, converting the primary amine end groups to negatively charged carboxylic acid groups. These carboxylated dendrimers did not detectably adsorb to silica from aqueous solution. TIR-FCS was used to determine their free-solution diffusion constants near silica surfaces, and the corresponding hydrodynamic radii compare favorably with values reported from forced Rayleigh scattering measurements.     

Poly(hydroxybutyrate-co-hydroxyvalerate) microspheres loaded with atrazine herbicide: screening of conditions for preparation,physico-chemical characterization,and in vitro release studies

Due to their widespread use in agriculture as well as in urban areas, agricultural chemicals are globally some of the most commonly encountered substances in waters. The objective of this study is to develop (including preparation and characterization) a new modified release system for the herbicide atrazine, employing poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) microspheres. The microspheres were prepared by the emulsification/solvent evaporation method, emulsifying an organic phase (atrazine and PHBV dissolved in chloroform) into an aqueous phase containing polyvinyl alcohol (PVA) as surfactant, under stirring, and then evaporating the solvent. A 2^4-1 fractional factorial design, investigating the influence of four variables at two levels, was performed to obtain formulations with optimized association efficiencies. There was a greater dependence of association efficiency on PVA concentration (negative) and the mass of polymer (positive) with lesser influence of both stirring speed and organic phase volume. The size of the particles was assessed using scanning electron microscopy, which showed that the particles were rough-surfaced spheres. The results obtained are promising, since the formulations presented encapsulation efficiency near 25% and the release kinetics profile of atrazine was altered when it was encapsulated in the microparticles, indicating that these systems may be efficient in reducing the environmental impact caused by the herbicide, hence making it safer to use.