The effect of high dose of gamma-irradiation on residual radicals concentration in ultra-high molecular weight polyethylene (UHMWPE) in the presence of vitamin E

Powder samples of UHMWPE (GUR 1020) containing 0.1% by wt. vitamin E (??-tocopherol, ??-T) were irradiated at room temperature in air for doses of 30-kGy, 65-kGy or 100-kGy (⁶⁰Co). After irradiation, they were stored at ?78.5°C (dry ice temperature) for one year and then opened to air at room temperature. Following the decay of the primary alkyl and allyl radicals (at room temperature in air), growth of the carbon-centered polyenyl R1 (?^·CH?CH=CH?, m ?? 3), and the oxygen-centered dior tri-enyl R2 (?^·OCH?CH=CH? _m , m ?? 3) residual radicals were measured for eight weeks. An X-band electron spin resonance (ESR) spectrometer was used for radical measurements. The initial relative radical concentrations (R2/R1) were found to be 10.13, 4.6 and 3.7 for the 65-kGy, 30-kGy and 100-kGy samples, respectively. R1 and R2 were both found to grow significantly in the 65-kGy samples while they grew only slightly in the 30-kGy and 100-kGy samples. In 65-kGy sample, R1 grew faster than R2 and the relative concentration R2/R1 was reduced from 10.13 to 2.9 for the 65-kGy sample while that for the 30-kGy and 100-kGy samples reduced only slightly, from 4.6 to 3.5 and 3.7 to 3.2, respectively. The behavior of the residual radicals can be explained by Raman spectroscopic data which suggest that the 65-kGy samples had a higher percentage of amorphous regions when compared to the 30-kGy or 100-kGy (21.7% compared to 15.7% or 17.9%) and also suggest a lower percentage of inter-phase regions (16.4% compared to 25.6% or 17.5%) and a lower level of structural disorder (0.26% compared to 0.44% or 0.27%).     

Preparation of Cs2ZrO3 and Cs2ThO3 Through Sol-gel Method and Their Characterization

Cesium zirconate and cesium thorate were prepared by sol-gel method following citrate-nitrate route. The compounds were characterized by X-ray diffraction, chemical analysis and simultaneous TG-DTA. The methods of preparation of Cs₂ZrO₃ and Cs₂ThO₃ reported in literature involve difficult steps and require stringent experimental conditions for obtaining the compounds. In this work we report an easier method for the preparation of these compounds at relatively low temperature. This revised version was published online in July 2006 with corrections to the Cover Date.     

A High Yielding, One-pot Synthesis of Substituted Ureas from the Corresponding Amines Using Mitsunobu’s Reagent

Summary. A Mitsunobu-based protocol has been developed for the synthesis of symmetrically and unsymmetrically substituted ureas from a variety of primary and secondary amines using gaseous carbon dioxide, in good to excellent yields. This protocol is mild and efficient compared to other reported methods.     

Grafting Vinyl Monomers onto Wool Fibers. VII. Graft Copolymerization of Methyl Methacrylate onto Wool Using Peroxydiphosphate-Thiourea Redox System

Graft copolymerization of methyl methacrylate onto wool was investigated in aqueous solution using the potassium peroxy-diphosphate-thiourea redox system as the initiator. The rate of grafting was determined by varying the monomer, peroxydi-phosphate ion, temperature, and solvent. The graft yield increases with increasing peroxydiphosphate ion up to 80 × 10^?-⁴ mol/L, and with further increase of peroxydiphosphate ion the graft yield decreases. The graft yield increases with increasing monomer concentration. The percentage of grafting decreases with increasing thiourea concentration. The rate of grafting increases with an increase of temperature. The effect of acid and water-soluble solvent and certain salts on graft yield has been investigated and a suitable rate expression has been derived.     

Siloxane polymers containing azo moieties synthesized by click chemistry for photo responsive and liquid crystalline applications

Three new types of siloxane‐based photoactive liquid crystalline polymers containing azo side groups were synthesized through the click chemistry route. The polymers having molecular weight range of 14,000–34,000 g mol^?1 were soluble in most of the polar solvents like chloroform, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, and dichloromethane. The photoresponsive trans–cis photoisomerization under UV radiation and cis–trans relaxation process in dark for the polymers were studied. The isomerization rate constants were found to be 0.01–0.04 sec^?1 and 1.16*10^?4–4.67*10^?4 sec^?1, respectively. It has been noted that the polymers showed high intensity absorption for n‐π* in chloroform. Both trans and cis forms of azide monomers having azo moiety exhibited molar extinction coefficient ( ? _max) in the range of 22,000–33,000 L mol^?1 cm^?1. The thermotropic behavior of the polymers was studied by polarizing optical microscope (POM) and differential scanning calorimetry (DSC) experiments. Polymer P1 showed liquid crystalline textures of nematic droplets, whereas P2 showed smectic focal conic texture and nematic droplets. Polymer P1 was also studied for photomechanical bending on exposure to UV radiation. The polymers showed initial degradation temperature in the range of 210–275°C. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Click chemistry‐based synthesis of azo polymers for second‐order nonlinear optics

Four linear polymers containing pendant azo moiety were synthesized through click chemistry for second‐order nonlinear optical study. The polymers were found soluble in most of the polar organic solvents such as tetrahydrofuran (THF), chloroform, and dimethyl formamide (DMF). The polymers showed thermal stability up to 300 °C and glass transition temperatures (T_g) in the range of 120–140 °C. The molecular weights (M_w) of these polymers (measured by gel permeation chromatography) were in the range 37,900–55,000 g/mol. The polymers were found to form optically transparent films by solution casting from THF solution. Order parameters were calculated from UV–vis absorption spectra. The morphology changes in the films after poling were characterized by atomic force microscopy. The angular dependence, temperature dependence, and time dependence of second harmonic generation (SHG) intensity were obtained by using 1064 nm Nd:YAG laser. The SHG intensity remained unchanged up to 95 °C. At room temperature, it remained stable up to 8 days after initial drop of about 14%. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthetic Studies Toward the Preparation of Phosphonate Analogs of Sphingomyelins and Ceramide 1 -Phosphate Using Pentacovalent Organophosphorus Methodology

Abstract

Non-isosteric phosphonate analogs of sphingomyelin and ceramide 1-phosphate are being synthesized from the condensation product of a pentacovalent oxaphospholene and azodicarboxylates. Model studies are initially described.     

Long distance atomic teleportation with as good success as desired

Long distance atomic teleportation (LDAT) is of prime importance in long distance quantum communication. Scheme proposed by Bose et al. (1999) in principle enables us to have LDAT using cavity decay. However it gives message state dependent fidelity and success rate. Here, using interaction of entangled coherent states with atom–cavity systems and a two-step measurement, we show how, LDAT can be achieved with unit fidelity and as good success as desired under ideal conditions. The scheme is unique in that, the first measurement predicts success or failure. If success is predicted then second measurement gives perfect teleportation. If failure is predicted the message-qubit remains conserved therefore a second attempt may be started. We found that even in presence of decoherence due to dissipation of energy our scheme gives message state independent success rate and almost perfect teleportation in single attempt with mean fidelity of teleportation equal to 0.9 at long distances. However if first attempt fails, unlike ideal case where message-qubit remains conserved with unit fidelity, in presence of decoherence the message-qubit remains conserved to some degree, therefore mean fidelity of teleportation can be increased beyond 0.9 by repeating the process.