KINETICS AND MECHANISM OF THE REACTION BETWEEN OLIGOSILOXANES AND P-TRICHLORO-N-DICHLOROPHOSPHORYL MONOPHOSPHAZENE (Cl3P[dbnd]N-POCl2)

Abstract

³¹P NMR investigation has been made of the action of Cl₃P[dbnd]N-POCl₂(I) first on hexamethyldisiloxane (Me₃Si)₂O and then on oligosiloxanes Me₃Si-(OSiMe₂)_n-OSiMe₃ n = 2 and n=3. The reactions were carried out in bulk or in solution with molar ratios siloxane/(I) varying from I to 5. It was demonstrated that only the monosubstitution of a chlorine atom by the -(OSiMe₂)_n,-OSiMe₃ species n = 0, 2, 3 with elimination of trimethylchlorosilane occurred leading to the derivatives Cl₂OP-N[dbnd]PCl₂O(SiMe₂-O)_nSiMe₃ (II). For n=2, 3 the siloxane redistribution reactions were observed by ²⁹Si NMR analysis. A two steps mechanism is proposed. consisting in a nucleophilic substitution, involving a tricoordinate phosphazenium intermediate, followed by the formation of an active ionic centre probably an oxonium ion, arising from the solvatation by the siloxane of this phosphazeniurn ion and /or of (II) leading to the redistribution reactions. The influences of the solvent, of trimethylchlorosilane, of the temperature, and of the addition of a protonated species (MDH) were investigated.     

Bianchi Type-III Cosmological Models with Time Dependent Displacement Vector for Barotropic Fluid Distribution in Lyra Geometry

Bianchi Type-III cosmological models for perfect fluid distribution with time dependent displacement field in the framework of Lyra geometry are investigated. To get the deterministic model of the universe, we have assumed two conditions (i) shear (σ) is proportional to the expansion (θ). This leads to B=C ⁿ where B and C are metric potentials and n is a constant. (ii) Universe is filled with barotropic fluid distribution which leads to p=γ ρ, 0≤γ≤1, p being isotropic pressure and ρ the energy density. The physical and geometrical aspects of the model with a special case and singularities in the models are also discussed.     

<Emphasis Type="Italic">C</Emphasis>-field Cosmological Models with Variable <Emphasis Type="Italic">G</Emphasis> in FRW Space–Time

C-field cosmological models based on Hoyle-Narlikar theory with variable gravitational constant G in the frame work of FRW (Friedmann-Robertson-Walker) space–time for positive and negative curvatures are investigated. To get the deterministic solutions in terms of cosmic time t, we have assumed G=R ⁿ and discussed for n=−1, −2, R being scalar factor. In both the cases, creation field C increases with time, the gravitational constant G and matter density (ρ) decrease with time in the model (21). In the model (41) G decreases with time and matter density (ρ) is constant. The other physical aspects of the models are also discussed.     

Ultratrace Analysis of Dopamine Using a Combination of Imprinted Polymer-Brush-Coated SPME and Imprinted Polymer Sensor Techniques

A combination approach in solid-phase microextraction, based on a molecularly imprinted polymer-brush coating on an optical fiber coupled with a complementary molecularly imprinted polymer sensor, has been adopted for isolation, preconcentration, and analysis of dopamine at ultratrace levels in highly dilute aqueous samples. This combination enabled enhanced (up to 8.5-fold) preconcentration of the analyte, which is appropriate for achieving a stringent detection limit in clinical diagnosis of several neurodegenerative diseases. The detection limit of dopamine in biological samples was 0.018 ng mL^?1 with a relative standard deviation less than 2.1% and without any non-specific contributions.     

Inflationary Scenario in Bianchi Type I Space-Time

Inflationary scenario in Bianchi Type I space-time is discussed. To get the deterministic model of the universe, it has been considered that the energy-momentum tensor of particles ∼T ⁴, almost vanishes in the course of expansion of universe and total energy-momentum tensor reduces to vacuum stress tensor. This leads to a∼e ^Ht where a is scale factor and H the Hubble constant and effective potential V(φ)=constant where φ is Higg’s field and n is a constant. The physical and geometrical aspects of the model in the context of inflationary scenario are also discussed.     

Ultratrace analysis of uracil and 5‐fluorouracil by molecularly imprinted polymer brushes grafted to silylated solid‐phase microextraction fiber in combination with complementary molecularly imprinted polymer‐based sensor

Main inborn errors of metabolism diagnosable through uracil (Ura) analysis and the therapeutic monitoring of toxic 5‐fluorouracil (5FU) in dihydro pyrimidine dehydrogenase (DPD) deficient patients require a sensitive, reproducible, selective and accurate method. In this work, an artificial receptor in the format of molecularly imprinted polymer (MIP) brush ‘grafted to’ the surface of sol–gel immobilized on cost‐effective homemade solid‐phase microextraction (SPME) fibers, individually imprinted with either of Ura and 5FU, was used in combination with a voltammetric sensor duly modified with the same MIP. This combination provided up to 10‐ and 8.4‐fold preconcentrations of Ura and 5FU, respectively, which was more than sufficient for achieving stringent detection limits in the primitive diagnosis of uracil disorders and fluoropyrimidine toxicity in DPD‐deficient patients. The proposed method permits the assessment of Ura and 5FU plasma concentrations with detection limits pf 0.0245 and 0.0484 ng mL^?1 (RSD = 1.0–2.5%, S/N = 3), respectively, without any problems of non‐specific false‐positives and cross‐reactivities in complicated matrices of biological samples. Copyright © 2008 John Wiley & Sons, Ltd.     

Influence of the dopant concentration in In-doped SrTiO3 on the structural and transport properties

thin films are grown epitaxially on NdGaO₃ (001) and characterized for x=0, 0.005, 0.02, 0.1, 0.2, 0.5. While films with x=0, 0.2 and 0.5 are insulating, the ones with x=0.005, 0.02 and 0.1 are semiconducting and show a p-type behaviour. Highly rectifying diodes composed of SrIn_0.005Ti_0.995O₃ grown on SrNb_0.02Ti_0.98O₃ thin films confirm this behavior. Therefore the use of In as a dopant in SrTiO₃ is promising in the field of semiconductors.     

An anisotropic magnetized viscous fluid cosmological model in general relativity

We investigate the behavior of a magnetic field in a viscous fluid cosmological model where the free gravitational field is of Petrov type D and the coefficient of shear viscosity is proportional to the rate of expansion in the model. Also discussed are the behavior of the model when the magnetic field tends to zero and some other physical properties.