Interconnected bis-silylenes: a new dimension in organosilicon chemistry

The past two decades have brought remarkable advances in organosilicon chemistry with the isolation of stable silylenes, persila-allene, and disilynes. The extension of this list gives an impression that it will continue to flourish. The judicous employment of sterically appropriate ligands has enabled the synthesis and isolation of compounds with low-valent silicon. Recently, for example, interconnected bis-silylenes were isolated where the two Si atoms are connected by a σ-bond and each Si atom is possessing a lone pair of electrons. The formal oxidation state of each Si atom in the interconnected bis-silylene is +1, so bis-silylenes can be considered as the valence isomers of disilynes. In this Account, we describe the synthesis of interconnected bis-silylenes and assess their potential as a new building block in organosilicon chemistry. In 2009, we reported the isolation of a bis-silylene ((PhC(NtBu)(2))(2)Si(2)) stabilized by a sterically bulky benz-amidinato ligand with tBu substituents on the nitrogen atoms. Prior to our work, Robinson and co-workers described the synthesis of a N-heterocyclic carbene stabilized bis-silylene. In following years, just two more interconnected bis-silylenes have been reported. Density functional theory calculations to establish the geometric and electronic structures of the reported bis-silylenes have shown that the Wiberg bond index (WBI) for all the reported bis-silylenes is ~1. The synthesis of stable (PhC(NtBu)(2))(2)Si(2) prompted explorations of its reactivity. An important facet of silylene chemistry involves oxidative addition at the Si(II) center with unsaturated substrates, a reaction also available for bis-silylenes. Due to the three reaction sites (two lone pairs of electrons and a labile Si(I)-Si(I) single bond) in the interconnected bis-silylenes, we expect novel product formation. A labile Si-Si bond facilitates the reactions of (PhC(NtBu)(2))(2)Si(2) with diphenyl alkyne or adamantyl phosphaalkyne which afforded 1,4- disilabenzene and 1,3-disilacarbaphosphide (CSi(2)P) derivatives, respectively. The former is a noteworthy addition to the silicon analogues of benzene, and the latter serves as a heavy cyclobutadiene. With white phosphorus, a cyclic Si(2)P(2) derivative, an analogue of cyclobutadiene was obtained. The most predominant structural feature of these heavy cyclobutadienes is the presence of two-coordinate P atoms.     

Spheroidization of metal and ceramic powders in thermal plasma jet

In the present investigation, a theoretical estimation of the percentage of spheroidization of particles has been made from basic fluid dynamic equations. Particles of different sizes were considered at different plasma gas flow rates and temperatures (input power). Particle inflight residence and melting times were calculated and using them, percentage of spheroidization was estimated. Spheroidization was found to be strongly dependent on particle size and plasma jet temperature.     

Dynamical characteristics of wave-excited channel flow

This paper is part of a study on the receptivity characteristics of the shear flow in a channel whose walls are subjected to a wave-like excitation. The small amplitude forced wavy wall motion is characterised by a wave number vectorλ ₁,λ ₂ and a frequencyω _g . The basic flow in the problem is a superposition of the Poiseuille flow and a periodic component that corresponds to the wave excitation of the wall. The aim of the study is to examine the susceptibility of this flow to transition. The problem is approached through studying the stability characteristics of the basic flow with respect to small disturbances. The theoretical framework for this purpose is Floquet theory. The solution procedure for solving the eigenvalue problem is the spectral collocation method. Preliminary results showing the influence of the amplitude and the wave number of the wall excitation on the stability boundary of the flow are presented.     

Investigation of the reaction impurities associated with methylamphetamine synthesized using the Nagai method

The synthesis of methylamphetamine hydrochloride from l-ephedrine or d-pseudoephedrine hydrochloride via reduction with hydriodic acid and red phosphorus was investigated. Eighteen batches of methylamphetamine hydrochloride were synthesized in six replicate batches using three different reaction times. This allowed the investigation of the variation of impurities in the final product with reaction time. The results obtained have resolved previously conflicting impurity profile data reported in the literature for this synthesis route. The impurity profile was shown to change with reaction time, and all previously reported impurity components were identified but not in all batches. Additionally, 20 batches of methylamphetamine hydrochloride were synthesized from either from l-ephedrine or d-pseudoephedrine hydrochloride in reactions which were allowed to proceed for 24 h. The impurities present in the resulting batches were investigated, and route-specific impurities present in all batches were identified. Batch-to-batch fluctuations in the resultant chromatographic impurity profile, despite careful synthetic monitoring and control, were also noted.     

Two-dimensional optical orthogonal codes for fiber-optic CDMA networks

Several constructions of two-dimensional (2-D) codes have been proposed to overcome the drawbacks of nonlinear effects in large spread sequences of one-dimensional (1-D) unipolar codes in fiber-optic code-division multiple-access (FO-CDMA) networks. Wavelength-time (W/T) encoding of the 2-D codes is practical in FO-CDMA networks. W/T codes reported so far can be classified mainly into two types: 1) hybrid codes, where one type of sequence is crossed with another to improve the cardinality and correlation properties and 2) conversion of 1-D sequences to 2-D codes to reduce the "timelike" property. This paper describes the basic principles of a new family of wavelength/time multiple-pulses-per-row (W/T MPR) codes, for incoherent FO-CDMA networks, which have good cardinality, spectral efficiency, and minimal cross correlation values. In addition, an expression for the upper bound on the cardinality of W/T MPR codes is derived. Another feature of the W/T MPR codes is that the aspect ratio can be varied by a tradeoff between wavelength and temporal lengths. The correlation properties of W/T MPR codes are verified by simulation using Matlab. For given wavelength /spl times/ time dimensions, various W/T codes, whose cardinalities are known, are compared, and it is shown that the W/T MPR family of codes have better cardinality and spectral efficiency than the other W/T codes. Performance analysis of the W/T MPR codes and their limiting cases is carried out for various parameter variations such as the dimensions of wavelength, time, and weight of the code.     

Game theory and fuzzy based back off algorithm for MAC protocol for multi traffic flows in ad hoc networks

Wireless Networks - In MAC protocols of wireless ad hoc networks, there may be collisions due to traffic load and it results in more energy consumption, delay and reduces throughput. In order to...     

Design of a new family of two-dimensional codes for fiber-opticCDMA networks

We report the design of a new family of two-dimensional codes for fiber-optic CDMA networks. These newly designed temporary/spatial single-pulse-per-row (T/S SPR) codes have out-of-phase autocorrelation zero and cross correlation equal to one. Optical orthogonal codes (OOCs) have the lowest out-of-phase autocorrelation and cross-correlation values (both equal to one) among the one-dimensional codes. We compare the performance of our codes to the OOC's for a given probability of error. Experimentally we verify the autocorrelation and cross-correlation properties of our codes     

A novel method of optical detection using a capacitive device

This paper describes a new method of optical detection, which essentially involves the measurement of the change in charge spectrum of MOS capacitors with incident light. It also suggests a symmetric insulator-semiconductor-insulator (ISI) structure for an efficient optical detector