Novel method of deoxidation of alcohols and its use in synthesis of covalent perchlorates

Alcohols can be effectively deoxidated by treatment with chlorine and sulfur in the presence of pyridine with incorporation of an external nucleophile from added salts.     

Template copolymerization near a patterned surface: computer simulation

We perform a Monte Carlo simulation of irreversible template copolymerization near a chemically heterogeneous surface with a regular distribution of discrete adsorption sites that selectively adsorb from solution one of the two polymerizing monomers and the corresponding chain segments. In the polymerization model, the chain propagation process is simulated by adding individual monomers to the end of growing macroradical. We focus in this paper on the influence of polymerization rate, adsorption energy, and the distance between adsorption sites on the chain conformation and the primary sequence of the resulting two-letter (AB) copolymers and, specifically, on the coupling between polymerization and adsorption. The conditions for the realization of conformation-dependent copolymerization are formulated. For this regime, we observe the formation of a quasiregular copolymer with two types of alternating sections. One of them contains randomly distributed A and B segments. The second one consists mainly of strongly adsorbed A segments. It is found that the average length of the random sections is proportional to the distance between the nearest neighbor adsorption sites. The average length of the A-rich sections is determined by the "adsorption capacity" of adsorption site. By varying the strength of the effective monomer-substrate interaction and the distribution of adsorption sites on the substrate, the copolymers with different surface-induced primary sequences can be designed and synthesized in a controlled fashion.     

Kinetics of destruction of diisopropyl methylphosphonate in corona discharge

The kinetics of the destruction of diisopropyl methylphosphonate (DIMP) in corona discharge has been studied using a flow tubular coaxial wire dielectric barrier corona discharge reactor. The identification and quantitative determination of DIMP, its destruction intermediates, and phosphorus‐containing destruction products were performed using molecular beam mass spectrometry and gas chromatography/mass spectrometry. Active discharge power was varied in the range 0.01–5 W. The destruction products such as isopropyl methylphosphonate, methylphosphonic acid, and orthophosphoric acid were found on the reactor walls. The dependence of the extent of the destruction, D (D = 1 ? X / X₀, where X and X₀ are DIMP mole fractions at the outlet and the inlet of the reactor), on the specific energy deposition E_x (E_x = PF^?1 X₀^?1, where F is the carrier gas flow and P is the power dissipated in discharge reactor) was measured over the DIMP mole fraction range 60–500 ppm at the pressure of 1 bar and the temperature of 340 K. Over the range of the experimental conditions studied the destruction obeys the “pseudo‐first‐order” kinetic law: ln(1 ? D) = ?KE_x. Plausible mechanisms of the destruction are discussed. It was concluded that ion mechanism is the major one responsible for the destruction process. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 331–337, 2002     

Frozen Friedel-Krafts Type Reaction of Phosphorus Halides with Tetraphenylborate Anion

Abstract

The Friedel-Krafts type reaction of phosphorus halides are well known and widely used in organic synthesis. Usually it requires catalyst and elevated temperature and spreads on the most electrophilic phosphorus halides.     

Analysis of point-target detection performance based on ATF and TSF

In many real applications such as remote sensing and space surveillance, traditional method based on ideal imaging has already been well-established. It is widely applied to analyze point-target detection performance of electro-optical imaging system, including signal-to-noise ratio (SNR) and noise equivalent temperature difference (NETD). However, this method cannot accurately predict these performance parameters, as it fails to take into account the influence of optical blurring caused by atmospheric turbulence, optics diffraction, optical aberrations, etc. In this sense, the methods, if proposed to thoroughly incorporate degrading factors into object acquisition model, would succeed to describe point-target detection performance to more degree of accuracy. The main focus of this article is to quantitatively analyze the influence of optical blurs upon point-target detection, and to establish close relationship between optical blurring and metrics of point-target acquisition. This point can be interpreted and achieved mathematically: the mathematical analysis based on image acquisition model is to combine Aperiodic Transfer Function (ATF) and Target Size Function (TSF) with analysis of SNR and NETD. In addition, the concept of NETD, traditionally used to describe extended object detection, is generalized and equivalently applied to analyze point-target detection. This refined method can be directly and conveniently used for faithfully predicting detection performance, and provides a more reliable benchmark for improving measurement setup, if we properly estimate the degree of image distortion.     

Volt-Watt Sensitivity of Semimetal BiSb Film Thermocouple Sensors in the 8 mm Wavelength Range

The paper considers the experimental and analytical data on volt-watt characteristics of metal-semimetal BiSb film point contacts in 8 millimeter wavelength range. Analytical expressions have been obtained for the volt-watt sensitivity and the resistance of the metal-semimetal BiSb film point contacts. A thermoelectric millimeter wave range detector has been designed on the basis of the sensors; the performance is illustrated by experimentally determined volt-watt relations.     

Computer Simulations of Interpolyelectrolyte Complexes Formed by Star-like Polymers and Linear Polyelectrolytes

Complexes formed by star-like polymers of various topology and oppositely charged linear polyelectrolytes were simulated using Brownian dynamics technique. Structural properties and their dependence on the polyelectrotyte charge were investigated and compared with similar data for complexes with dendrimers. Remarkable overcharging was observed for all stars in complexes.     

Influence of solvent electron affinity on paramagnetic defects in hybrid Si/SiOx luminescent nanoparticles

Journal of Nanoparticle Research - One-dimensional silver telluride nanowires (NWs) as potential thermoelectric materials have been studied extensively. At present, most of the efforts are focused...