TSL and EPR studies of SrBPO5 doped with CeO2and co-doped with CeO2 and Sm2O3

Thermally stimulated luminescence (TSL) and electron paramagnetic resonance (EPR) investigations were carried out on gamma irradiated SrBPO₅ samples doped with CeO₂ and co-doped with CeO₂ and Sm₂O₃. On gamma-irradiation at room temperature, BO₃ ^2–, O₂ ^– and O^– radicals were produced. It was seen that the O^– radical ion disappeared in the sample annealed at 500 K. It is proposed that the recombination between trapped electrons and O^– radical ions results in transfer of recombination energy to the impurity centre Ce³⁺ resulting in TSL glow peak at 485 K. In the case of co-doped samples energy transfer occurs between Ce³⁺ to Sm³⁺ resulting in increase in the intensity of glow peak at 485 K.The authors are grateful to Dr. V. K. Manchanda, Head, Radiochemistry Division, BARC for his keen interest and encouragement during the course of this work.     

Global variations in peak bone mass as studied by dual-energy X-ray absorptiometry

In 1994, the International Atomic Energy Agency (IAEA) initiated a 5-year Co-ordinated Research Project (CRP) to determine geographical and racial differences in peak bone mineral density (BMD) in men and women aged 15-49 years. The study demonstrates that there are distinct global differences in BMD at the hip and spine in both men and women approximating to one population standard deviation between populations with the highest and lowest BMD. These differences persist following adjustments for age, sex and body size. Such information is valuable in understanding the reasons for global differences in fracture rate and predicting future trends in fracture incidence. This revised version was published online in August 2006 with corrections to the Cover Date.     

An 227Ac-211Pb generator for test experiments of solution chemistry of element 114

A simple and effective method has been developed for the continuous production of the short-lived isotope Pb as a homolog of element 114 on the principle of a radionuclide generator. The method is based on the initial sorption of ²²⁷Ac or ²²³Ra on a small cation-exchange column, with subsequent “milking” of ²¹¹Pb (36.1 m) by a mixture of HCl/CH₃OH. The optimum conditions for the repeated separation of ²¹¹Pb from radionuclides strongly sorbed by the cation-exchanger (Ac, Th, Ra, Pu, TPE) have been determined. Possibilities of using the ²¹¹Pb generator for test experiments on the solution chemistry of element 114 have been shown. Advantages of aqueous alcohol HCl solutions for the isolation of ²¹¹Pb (element 114) are discussed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Photoinitiators with functional groups. VII. Covalently bonded camphorquinone—amines

Camphorquinone (CQ), a widely used photoinitiator (PI) in dental applications, was covalently bonded to aromatic amines to enhance the rate of electron and proton transfer effect due to the close vicinity of the diketone and the amine group. 10‐bromocamphorquinone and 10‐bromomethylcamphorquinone were selected as suitable precursors for esterification with the carboxyl group containing aromatic amines based on 4‐dimethylaminobenzoic acid. Properties of the new photoinitiating systems were investigated by UV spectroscopy and differential scanning photocalorimetry in lauryl acrylate. Compared to physical mixtures, in all cases similar or even better performance was obtained. Surprisingly, 10‐acetyl derivatives 7 – 9 and 18 especially, were found to be highly reactive. Compared to CQ/ethyl 4‐dimethylaminobenzoate, the rate of photopolymerization was increased by a factor of up to 2. Intramolecular reaction was confirmed by photo‐differential scanning calorimetry experiments with varying PI concentrations. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4948–4963, 2004     

Novel dinitroxide mediating agent for stable free‐radical polymerization

A novel dinitroxide mediating agent that was suitable for stable free‐radical polymerization was synthesized and used in the block copolymerization of styrene and t‐butyl styrene. Quantitative yields of a novel dinitroxide based on 1,6‐hexamethylene diisocyanate and 4‐hydroxy‐2,2,6,6‐tetramethyl‐1‐piperidinyloxy were obtained. Various experimental parameters, including the nitroxide‐to‐initiator molar ratio, were examined, and it was determined that the polymerization was most controlled under conditions similar to those of conventional 2,2,6,6‐tetramethyl‐1‐piperidinyloxy‐mediated stable free‐radical polymerization. Moreover, the dinitroxide mediator proved to be a viable route for the facile two‐step synthesis of triblock copolymers of styrene and t‐butyl styrene. However, the dinitroxide mediation process resulted in a higher than expected level of nitroxide decomposition, which resulted in polymers possessing a terminal alkoxyamine and an adjacent hydroxylamine rather than a preferred internal bisalkoxyamine. This decomposition resulted in the formation of diblock copolymer species during the triblock copolymer synthesis. Gel permeation chromatography was used to monitor the chain‐end decomposition kinetics, and the determined observed rate constant (5.89 × 10^?5 s^?1) for decomposition agreed well with previous studies for other dinitroxide mediating agents. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1547–1556, 2004     

Synthesis and characterization of linear tetrablock quarterpolymers of styrene,isoprene, dimethylsiloxane,and 2-vinylpyridine

A series of five tetrablock quarterpolymers of styrene, isoprene, dimethylsiloxane, and 2-vinylpyridine with molecular weights varying from 117 × 10³ to 177 × 10³ and having different compositions were synthesized. The synthesis was based on recent advances in the controlled high-vacuum anionic polymerization of hexamethylcyclotrisiloxane and on the selective linking of poly(dimethylsiloxane)lithium with the chlorosilane group of the heterofunctional linking agent chloromethylphenylethylene dimethylchlorosilane. Combined characterization results by size exclusion chromatography, membrane osmometry, and NMR spectroscopy suggested that the synthesized multiblock multicomponent polymers had a high degree of structural and compositional homogeneity. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 514–519, 2004     

Atom transfer radical polymerization of methyl methacrylate by copper(I)‐pyridine‐2‐carboximidate catalysts

Pyridine‐2‐carboximidates [methyl ( 1a ), ethyl ( 1b ), isopropyl ( 1c ), cyclopentyl ( 1d ), cyclohexyl ( 1e ), n‐octyl ( 1f ), and benzyl ( 1g )] were prepared from the reaction of 2‐cyanopyridine with the corresponding alcohols. Cyclopentyl‐substituted 1d was found to be a highly effective ligand for copper‐catalyzed atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA). For example, the observed rate constant for a CuBr/ 1d catalytic system was found to be nearly twice as high as the cyclohexyl‐substituted CuBr/ 1e catalytic system [k_obs = (1.19 vs 0.56) × 10^?4 s^?1). The effects of the solvents, temperature, catalyst/initiator, and solvent/monomer ratio on the ATRP of MMA were studied systematically for the CuBr/ 1d catalytic system. The optimum condition for the ATRP of MMA was found to be a 1:2:1:400 [CuBr]_o/[ 1d ]_o/[ethyl 2‐bromoisobutyrate]_o/[MMA]_o ratio at 60 °C in veratrole solution, which yielded well‐defined poly(MMA) with a narrow molecular weight distribution of 1.14. The catalytically active copper complex 2d was isolated from the reaction of CuBr with 1d . Narrow molecular weight distributions as low as 1.06 were achieved for the CuBr/ 1d catalytic system by employing 10% of the deactivator CuBr₂. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2747–2755, 2004     

Hollow latex particles as submicrometer reactors for polymerization in confined geometries

A method was developed for free‐radical polymerization in the confines of a hollow latex particle. Hollow particles were prepared via the dynamic swelling method from polystyrene seed and divinylbenzene and had hollows of 500–1000 nm. So that these hollow poly(divinylbenzene) particles could function as submicrometer reactors, the particles were filled with a monomer (N‐isopropylacrylamide) via the dispersion of the dried particles in the molten monomer. The monomer that was not contained in the hollows was removed by washing and gentle abrasion. Free‐radical polymerization was then initiated by γ radiolysis in the solid state. Transmission electron microscopy showed that poly(N‐isopropylacrylamide) formed in the hollow interior of the particles, which functioned as submicrometer reactors. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5706–5713, 2004     

Adsorption Behaviour of 134Cs and 22Na Ions on Tin and Titanium Ferrocyanides

Tin and titanium ferrocyanides were studied as adsorbents for alkali metal ions, viz., ¹³⁴Cs and ²²Na, which represent radioactive wastes. The ferrocyanides were prepared in granular form. The tin version contained 11.2% water, while the titanium version contained 17.7% water. The exchange capacities for Cs⁺ and Na⁺ in the hydrated tin version were about 1.5 and 0.7 meq/g, respectively, while those in the titanium version were 2.2 and 1.2 meq/g, respectively. Drying at 250°C decimated those capacities. The diffusional time constant of Cs⁺ at 25°C, determined via Fick's second law, was of order of magnitude 1 × 10^–3 s^–1, though there were minor differences due to particle size and the form of ferrocyanide. Similarly, the effective diffusivity was of order of magnitude 1 × 10^–8 cm²/s. The titanium version responded slightly faster than the tin version. Likewise, equilibrium measurements in mixtures with sodium nitrate, potassium nitrate, or uranium oxide, showed that the titanium version exhibited significantly greater selectivity for Cs⁺ than did the tin version. Unfortunately, tests of complete elution of the Cs⁺ from the ferrocyanides were mostly disappointing. Work continues on that subject.     

Analysis of Glycosides and Aglycones of Flavonoid Compounds by Double-Development Thin-Layer Chromatography

JPC – Journal of Planar Chromatography – Modern TLC - Flavonoid glycosides are much more polar than their aglycones and the two groups of compounds are difficult to separate by planar...