Synthesis of enantiomerically pure anti-1,2-diaryl and syn-1,2-alkylaryl vic-selenoamines

Phenylselenyl benzylcarbanion stabilized by an (S)-2-p-tolylsulfinyl group evolves in a highly stereoselective way in the reactions with (S)-N-(p-tolylsulfinyl)imines at -98 °C affording diastereomerically pure 1,2-selenoamino derivatives in good yields. The syn or anti relationship of the obtained compounds depends on the alkyl or aryl character of the imine. They are easily transformed into enantiomerically pure (1R,2S)-1-aryl[or (1S,2S)-1-alkyl]-2-(phenylseleno)-2-phenylethylamines by reaction with t-BuLi and subsequent methanolysis of the generated sulfinamide derivatives with TFA.     

Macrocycle formation by proton-template-induced dimerization of complexes with (alkoxoimino)pyridine

The existence of a strong hydrogen bond between two molecules of an (alkoxoimino)pyridinemanganese(I) complex induces their dimerization and the formation of a metallamacrocycle. The expected intramolecular attack of the alkoxo moiety is disfavored.     

Electron impact excitation of the ã (3)B(1u) electronic state in C2H4: an experimentally benchmarked system?

We report on differential and integral cross section measurements for the electron impact excitation of the lowest-lying triplet electronic state (a? (3)B(1u)) in ethylene (C(2)H(4)). The energy range of the present experiments was 9 eV-50 eV, with the angular range of the differential cross section measurements being 15°-90°. As the ground electronic state of C(2)H(4) is a (1)A(g) state, this singlet → triplet excitation process is expected to be dominated by exchange scattering. The present angular distributions are found to support that assertion. Comparison, where possible, with previous experimental results from the University of Fribourg group shows very good agreement, to within the uncertainties on the measured cross sections. Agreement with the available theories, however, is generally marginal with the theories typically overestimating the magnitude of the differential cross sections. Notwithstanding that, the shapes of the theoretical angular distributions were in fact found to be in good accord with the corresponding experimental results.     

The effect of the partial pressure of water vapor on the surface tension of the liquid water-air interface

Precise measurements of the surface tension of water in air vs. humidity at 5, 10, 15, and 20 °C are shown. For constant temperature, surface tension decreases linearly for increasing humidity in air. These experimental data are in good agreement with a simple model based on Newton's laws here proposed. It is assumed that evaporating molecules of water are ejected from liquid to gas with a mean normal component of the speed of "ejection" greater than zero. A high humidity in the air reduces the net flow of evaporating water molecules lowering the effective surface tension on the drop. Therefore, just steam in air acts as an effective surfactant for the water-air interface. It can partially substitute chemical surfactants helping to reduce their environmental impact.     

Asymmetric intramolecular pauson-khand reaction mediated by a remote sulfenyl or sulfinyl group

In this work, we report the use of the asymmetric intramolecular Pauson-Khand reactions of 4-aryl-4-cyano-1,6-enynes for obtaining enantiomerically enriched bicyclo[3.3.0]octenones, and the influence of both the quaternary stereocenter and the sulfur functions located at ortho-position of the aryl group, on their stereoselectivity and reactivity. The sulfenyl derivatives bearing substituted or unsubstituted triple bonds and mono- and disubstituted alkene moieties afford bicyclo[3.3.0]octenones in high yields with complete diastereocontrol. These results are explained by assuming the association of the lone electron pair at sulfur to the Co-alkyne complexes.     

A New Calibration Method for the Accurate Determination of Ethylene Content in Ethylene-Propylene Copolymers by CRYSTEX-IR

Summary: CRYSTEX is a fully automated instrument for the determination of Xylene Solubles in polypropylene and ethylene-propylene copolymers, providing an excellent correlation with gravimetric methods. The instrument can be equipped with a dual band infrared (IR) detector to quantify the ethylene weight percentage (C2%) in the amorphous fraction, and in the whole polymer sample. In this work, a new approach based on multiple linear regression (MLR) models is presented, which makes use of two independent IR absorbance signals acquired simultaneously by the detector. A compromise model to predict directly C2% is proposed, which balances good accuracy and reduced experimental effort. MLR models able to predict the total sample concentration were also developed. The results were successfully validated using copolymer standards in a wide chemical composition range.     

A complete diophantine characterization of the rational torsion of an elliptic curve

We give a complete characterization for the rational torsion of an elliptic curve in terms of the (non-)existence of integral solutions of a system of diophantine equations.     

Representable Monotone Operators and Limits of Sequences of Maximal Monotone Operators

We show that the lower limit of a sequence of maximal monotone operators on a reflexive Banach space is a representable monotone operator. As a consequence, we obtain that the variational sum of maximal monotone operators and the variational composition of a maximal monotone operator with a linear continuous operator are both representable monotone operators.     

Combined PIV/PLIF measurements of a steady density current front

A novel method for combined particle image velocimetry and laser induced fluorescence is described and results from an experiment in a stratified flow are presented. A standard two-dimensional, one camera particle image velocimetry configuration is used, acquiring images of the seeding particles and the dye marking the current simultaneously and separating the two fields digitally. The implementation of the postprocessing method, its capabilities and the necessary conditions for its use are discussed in detail. The proposed method is applied to an arrested density current front. The front is made stationary by opposing a uniform velocity profile, obtained from the combination of a moving floor and the recirculation of fresh water in the channel. To improve the quality of the images, the current is made optically homogeneous by matching the refractivity index throughout the domain. Instantaneous and time averaged fields are obtained for both velocity and density. Simultaneous measurements of these fields provide insight in the mixing processes at the front of the density current. In particular persistent billow generation, similar to that found in shear layers and associated with Kelvin–Helmholtz instabilities, is observed. Support for this work was partially provided by the US Office of Naval Research through the Coastal Geosciences Program and by Exxon Mobil Exploration Company. The authors would like to thank Dr. Wing Lai of TSI, Inc, for loaning part of the PIV equipment used in this study.