Acyclic diastereoselection in prochiral radical addition to prochiral olefins

The stereochemical preference (syn or anti) when prochiral radicals add to prochiral acceptors is of fundamental interest. The primary focus of this research was to determine which factors influence the relative stereochemistry between the beta and gamma chiral centers when these are formed concurrently. While moderate diastereoselectivity was found for addition of alkyl (6a-d) and alpha-alkoxy radicals (16a-c) (< or =6:1 syn) to acceptors 4, 7, 8, 10, and 14, consistently high selectivity was observed with less reactive halogenated radicals (6f,g) (>15:1 anti). Steric influence in alkyl radical additions was difficult to evaluate due to decreased reactivity when using bulky reaction partners; however, more reactive alpha-alkoxy radicals, it was found that increasing steric bulk leads to moderate increases in selectivity. In addition, higher selectivity was observed when employing lanthanide Lewis acids whose environment (reactivity) was modified using achiral additives, suggesting a potentially simple means for selectivity enhancements in radical reactions. Overall these results indicate that significant stereoelectronic effects are necessary to achieve high levels of selectivity in prochiral radical additions to prochiral acceptors.     

A Convenient Synthesis of 2-Amino-1,3- selenazoles Using Ionic Liquid and Microwave Irradiation

Abstract

A simple and environmentally benign synthesis of 2-amino-1,3-selenazoles by microwave irradiation using 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF₄) ionic liquid (IL) is described. Acyl halides, phenacyl halides, and α-bromo-β-keto esters easily undergo condensation with selenourea in ([Bmim]BF₄) by microwave irradiation to afford the desired products of good purity in excellent yields. The ionic liquid can be easily recovered and reused at least 10 times without losing its activity. The duration of the reaction ranges from 4–6 min.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.

GRAPHICAL ABSTRACT      

Visible fluorescence induced by the metal semiconductor transition in composites of carbon nanotubes with noble metal nanoparticles

We show that single-walled carbon nanotube (SWNT) bundles emit visible fluorescence in the presence of noble metal nanoparticles and nanorods in the solid state. Conductivity measurements with metallic nanotubes, isolated from pristine SWNTs, show that they become semiconducting in the presence of the metal nanoparticles. Nanoparticle binding increases the defects in the nanotube structures which is evident in the Raman spectra. The metal-semiconductor transition removes the nonradiative decay channels of the excited states enabling visible fluorescence. Nanotube structures are imaged using this emission with resolution below the classical limits.     

Longitudinal dynamics of a tracked vehicle: Simulation and experiment

In recent years virtual dynamic system simulation has become very important in the design and development stage, as new strategies can be examined without expensive measurements and with reduced time. This paper describes the development of a simulation model for transient analysis of the longitudinal dynamics of a heavy tracked vehicle. The driving inputs for this simulation model are obtained from a powertrain model. The main elements of the powertrain include the engine, Torque Converter (TC), transmission and drivetrain. Here the engine is modeled based on the engine maps from steady-state experiments. The TC is modeled based on its characteristic map from experiments. A fairly simple transmission model is used which is based on static gear ratios assuming small shift times. The final drivetrain model however includes the rotational dynamics of the sprocket. The simulation model developed is validated by comparing the predicted values with the measured data from experiments. The results have demonstrated that the developed model is able to predict fairly accurately the acceleration and braking performance of the heavy tracked vehicle on both soft and hard terrain.     

Non-resonant microwave absorption studies of superconducting MgB2 and MgB2 + MgO

Non-resonant microwave absorption (NRMA) studies of superconducting MgB₂ and a sample containing ∼10% by weight of MgO in MgB₂ are reported. The NRMA results indicate near absence of intergranular weak links in the pure MgB₂ sample. A linear temperature dependence of the lower critical field H _c1 is observed indicating a non-s wave superconductivity. However, the phase reversal of the NRMA signal which could suggest d wave symmetry is also not observed. In the MgB₂ + MgO sample, much larger low field dependent absorption is observed indicating the presence of intergranular weak links. The hysteretic behavior of NRMA is compared and contrasted in the two samples. In the pure MgB₂ sample, a large hysteresis is observed between the forward and the reverse scans of the magnetic field indicating strong pinning of flux lines. This hysteresis saturates a few degrees below T _c while in the MgB₂ + MgO sample, a much slower increase of hysteresis with decreasing temperature is observed, a signature of weaker pinning.     

Statistical group testing with queueing involved

We consider a queueing model in which items wait to undergo group testing in batches of sizem. However, if fewer thanm items are present at the beginning of a service, items are tested singly. Ifm or more items are waiting at such an epoch, a group of sizem is tested and, if the group passes the test, allm items leave the system. When a group is found to contain at least one defective item, them items in it are retested individually. An algorithm is developed to compute many steady-state probabilities related to this queue. Comparisons of these probabilities are used to assess the effect of the group sizem on the behavior of the queue of items waiting for testing.This research was supported in part by Grant Nr. ECS-8601203 from the National Science Foundation.     

On the formation of protected gold nanoparticles from AuCl<Stack><Subscript>4</Subscript><Superscript>−</Superscript></Stack> by the reduction using aromatic amines

Amines are used extensively as reductants and subsequent capping agents in the synthesis of metal nanoparticles, especially gold, due to its affinity to nitrogen. Taking 2-methyl aniline as an example, we show that metal reduction is followed by polymerization of the amine, while part of it covers the nanoparticle surface another fraction deposits in the solution. It is found that the oxidative polymerization of the amine goes in step with the formation of gold nanoparticles. The gold nanoparticles thus formed have a mean diameter of 20 nm. The polymerized amine encapsulates the gold nanoparticle forming a robust shell of about 5 nm thickness, making the gold core inert towards mineralizing agents such as chloroform, bromoform, sodium cyanide, benzylchloride, etc. which react with the naked gold nanoparticles. The deposited polymer is largely protonated, taking up protons from the medium during its formation. Similar results have been observed in the case of aniline also. The materials have been fully characterized by spectroscopy and microscopy.This revised version was published online in August 2005 with a corrected issue number.     

A convenient general method for the synthesis of hydroxy diacids

Olefinic aldehydes and epoxides with terminal double bonds react with Grignard reagents, and the acetates made from the resulting alcohols undergo double bond cleavage on treatment with RuCl₃·xH₂O in the presence of NaIO₄ to give acetoxy diacids. Hydrolysis with LiOH then affords hydroxy diacids.