Photoassisted vapor generation in the presence of organic acids for ultrasensitive determination of Se by electrothermal-atomic absorption spectrometry following headspace single-drop microextraction

A method is described for the determination of selenium at the pg/mL level by electrothermal-atomic absorption spectrometry using in situ photogeneration of Se vapors, headspace sequestration onto an aqueous microdrop containing Pd(II) and subsequent injection in a graphite tube. Several organic acids (formic, oxalic, acetic, citric and ethylenediaminetetraacetic) have been tried for photoreduction of Se(IV) into volatile Se compounds under UV irradiation. Experimental variables such as UV irradiation time, organic acid concentration, Pd(II) concentration in the drop, sample and drop volumes, extraction time and pH were fully optimized. Low-molecular weight acids such as formic and acetic provided optimal photogeneration of volatile Se species at a 0.6 mol/L concentration. Citric and ethylenediaminetetraacetic acid allowed to use a concentration as low as 1 mmol/L, but extraction times were longer than for formic and acetic acids. Photogeneration of (CH₃)₂Se from Se(IV) in the presence of acetic acid provided a detection limit of 20 pg/mL, a preconcentration factor of nearly 285 and a precision, expressed as relative standard deviation, of 4%. Analytical performance seemed to depend not only on the photogeneration efficiency obtained with each acid but also on the stability of the vapors in the headspace. The method showed a high freedom from interferences caused by saline matrices, but interferences were observed for transition metals at a relatively low concentration.     

An efficient forward–reverse expectation-maximization algorithm for statistical inference in stochastic reaction networks

In this work, we present an extension of the forward–reverse representation introduced by Bayer and Schoenmakers (Annals of Applied Probability, 24(5):1994–2032, 2014) to the context of stochastic reaction networks (SRNs). We apply this stochastic representation to the computation of efficient approximations of expected values of functionals of SRN bridges, that is, SRNs conditional on their values in the extremes of given time intervals. We then employ this SRN bridge-generation technique to the statistical inference problem of approximating reaction propensities based on discretely observed data. To this end, we introduce a two-phase iterative inference method in which, during phase I, we solve a set of deterministic optimization problems where the SRNs are replaced by their reaction-rate ordinary differential equations approximation; then, during phase II, we apply the Monte Carlo version of the expectation-maximization algorithm to the phase I output. By selecting a set of overdispersed seeds as initial points in phase I, the output of parallel runs from our two-phase method is a cluster of approximate maximum likelihood estimates. Our results are supported by numerical examples.     

Separately radial and radial Toeplitz operators on the projective space and representation theory

We consider separately radial (with corresponding group T ⁿ ) and radial (with corresponding group U(n)) symbols on the projective space P ⁿ (C), as well as the associated Toeplitz operators on the weighted Bergman spaces. It is known that the C*-algebras generated by each family of such Toeplitz operators are commutative (see R. Quiroga-Barranco and A. Sanchez-Nungaray (2011)). We present a new representation theoretic proof of such commutativity. Our method is easier and more enlightening as it shows that the commutativity of the C*-algebras is a consequence of the existence of multiplicity-free representations. Furthermore, our method shows how to extend the current formulas for the spectra of the corresponding Toeplitz operators to any closed group lying between T ⁿ and U(n).     

Is it possible to explore Peccei-Quinn axions from frequency-dependence radiation dimming?

We explore how the Peccei-Quinn (PQ) axion parameter space can be constrained by the frequency-dependence dimming of radiation from astrophysical objects. To do so we perform accurate calculations of photon-axion conversion in the presence of a variable magnetic field. We propose several tests where the PQ axion parameter space can be explored with current and future astronomical surveys: the observed spectra of isolated neutron stars, occultations of background objects by white dwarfs and neutron stars, the light-curves of eclipsing binaries containing a white dwarf. We find that the lack of dimming of the light-curve of a detached eclipsing white dwarf binary recently observed, leads to relevant constraints on the photon-axion conversion. Current surveys designed for Earth-like planet searches are well matched to strengthen and improve the constraints on the PQ axion using astrophysical objects radiation dimming.     

Morphology,distribution and abundance of antennal sensilla in three stink bug species (Hemiptera: Pentatomidae)

The neotropical stink bugs, Euschistus heros, Piezodorus guildinii and Edessa meditabunda, are important pests of soybean and other crops throughout Central America and in South America from Northern Argentina to Brazil. Mate finding and host plant location in these species depend largely on their chemical communication, and semiochemicals are important mediators of these behaviors. In this study scanning electron microscopy was used to examine the external morphology, distribution and abundance of antennal sensilla on males, females and 5th instar nymphs of these species. Nine morphologically different sensilla types were found: trichod sensilla, type 1 and 2 (ST1 and ST2), long and short basiconic sensilla (SB1, SB2, and SB3), slit-tipped and knob-shaped basiconic sensilla, long chaetic sensilla (Sch) and coeloconic sensilla (Sco). Differences were detected in the abundance and arrangement of the sensilla over the antennal segments in individuals of the same species and among the species studied. The Sch, Sco and the slit-tipped and knob-shaped basiconic sensilla accounted for the major difference in sensilla types among the species. The ST1 was the most abundant type and was restricted to the flagellum. The pedicel of E. heros differs from the pedicels of P. guildinii and E. meditabunda mainly by the absence of Sch. There was a sexual dimorphism in ST1, SB1 and SB2, and this may be an indicative of their roles in detection of male-produced sex pheromone and odors derived from the host plants. The SB2 was lacking in the antennal tip of both sexes and 5th instar nymphs, but was abundant on the second flagellar segment of females of the three species. The same types of sensilla were found on 5th instar nymphs, but always in significantly lower numbers. The morphology and putative functions of each sensilla were compared and discussed.     

The influence of the transition metal and the heteroatomic-bridge on the action of metallocene/methyl aluminoxane catalysts in ethylene polymerization and on the properties of the polymer

This work reports a comparative study of the catalytic behaviour for a series of metallocenes derived from Ti, Zr, Hf and Nb, which after activation with methylaluminoxane can polymerize ethylene. Results show that the Zr metallocene with a  (CH₃)₂Si Bridge presents the highest activity, and the metallocenes based on Hf and Nb do not show any significant activity under the tested conditions.     

New low viscous polyisocyanates for VOC compliant systems

Since 1961, aliphatic polyisocyanates based on HDI-biurets are used as light stable hardeners for 2-K polyurethane coatings. The market introduction of the HDI-isocyanurates or simply 'trimers' in the early 1980's was driven by their lower viscosity and their better monomer stability. The most recent development in HDI-polyisocyanate research are the iminooxadiazinediones (asymmetric trimers). In this paper, a new product based on that technology with a very low viscosity (700 mPas@23°C) and a NCO-functionality of more than 3 is presented. Because of its low viscosity, this hardener can be easily incorporated into aqueous systems and is the solution for high and full solids coatings as well.