Electron spin resonance study of γ-irradiated poly(acrylic acid)

Electron spin resonance (ESR) spectra of poly(acrylic acid) (PAA) γ-irradiated in air at room temperature and recorded at room temperature and at liquid-nitrogen temperature have been studied to identify the radiation products. The ESR spectra are composed of eight lines with hyperfine splittings of 23 ± 1 G and 11 ± 1 G. The method of least-squares total curve fitting, employing the Lorentzian line shape function, to the observed spectra enabled the assignment of the spectra. Computed spectra obtained by the superposition of a singlet and the spectra due to chain radicals are considered to give the best fits to the observed ESR spectra. The singlet is assigned to the radicals COOH, and the component 10-line spectra are assigned to the chain radicals CH₃? CH? CH₂ ～ and/or ～ CH₂? CH? CH₂ ～. The observed change in line shape with temperature of the ESR spectra is attributed to the hindered oscillations of the methyl groups about the C_α? C_β bond axis of the chain radicals. The existence of the methyl groups is confirmed by the measurement of infrared absorption.     

Study of the effect of swift heavy Ni ion irradiation on ruby single crystal by using the XANES and EXAFS techniques

We have made the XAFS measurements at the Cr–K-edge on natural Indian ruby single crystals (corundum) and its two irradiated samples with fluence 1×10¹² Ni⁶⁺ and 5×10¹² Ni⁶⁺ ions/cm². Irradiated samples show interesting changes in their physical appearance. XANES measurements show progressive decrease in Δ_oct value on increase of Ni fluence in irradiated samples. EXAFS measurements on these samples show decrease in Cr–O distance on increase of Ni fluence. Lowering of Δ_oct value is correlated with the increase of Cr–O distance.     

Spectroscopic studies of new model compounds for poly[N,N′-bis(phenoxyphenyl)pyromellitimide]

New model compounds for poly[N,N′-bis(phenoxyphenyl)pyromellitimide] have been synthesized in order to investigate the formation of imine bonds which are proposed to form during the curing process and lead to crosslinking in the bulk polymer. Raman studies show that terminal amines can react with imide carbonyls during curing to form C?N bonds. The Raman band due to C?N appears at 1656 cm^?1 and the band due to C?O closest to the imine bond is observed at 1742 cm^?1. These results are in agreement with previously published results on vapor deposited polyimide films.     

Montmorillonite KSF-catalyzed one-pot synthesis of hexahydro-1H-pyrrolo[3,2-c]quinoline derivatives

Aryl amines react with endocyclic ene-carbamates such as tert-butyl 2,3-dihydro-1H-1-pyrrolecarboxylate and tert-butyl 1,2,3,4-tetrahydro-1-pyridinecarboxylate, on the surface of montmorillonite KSF clay under mild conditions to afford the corresponding 3-aminopropylhexahydropyrrolo[3,2-c]quinoline or 4-aminobutyloctahydrobenzo[h][1,6]naphthyridine derivatives in excellent yields with moderate diastereoselectivity.     

Mössbauer hyperfine interactions in natural wolframites

Powdered samples of Indian Natural Wolframites, (Fe_xMn_1?x) WO₄ with x=0.95 to 0.41, obtained from seven different locations of two quartz-wolframite deposits of Degana and Sirohi in Rajasthan, have been investigated by Mössbauer spectroscopy down to 20K and magnetic susceptibility down to 77K. The Mössbauer spectra from 300K to 30K clearly indicate multiple sites which is at variance with the reported work. Below 50K a weak magnetic interaction with H_int～45Koe is observed. The spectra above transition temperature are resolved in three doublets and explained on the basis of reported crystal structure. The values of isomer shift, quadrupole splitting and magnetic hyperfine field have been attributed to high spin ferrous ions with octahedral symmetry. Relatively small value of Q.S. (～1.5 mm/sec. at 300K) indicate a strong contribution of the lattice term to the electric field gradient.     

X-ray fluorescence in some rare earth and high Z elements excited by 661.6 keV γ-rays

The K-shell X-ray fluorescence cross sections are determined experimentally for 10 elements such as Pb, Hg, Ir, W, Lu, Tm, Dy, Tb, Gd and Nd at excitation energy of 661.6 keV associated with γ-rays of ¹³⁷Cs radioisotope. The technique employed involves the measurement of total intensity of fluorescent K X-rays that follow the photoeffect absorption of a known flux of γ-rays using a well type Nal(Tl) detector. The obtained results are compared with the available theoretical values and other measured values.     

Excess enthalpies for mixtures of cyclohexanone with isomeric propanols and butanols at 298.15 K

Excess enthalpies (H ^E ) for mixtures of cyclohexanone with propan-1-ol. propan-2-ol, butan-1-ol, butan-2-ol and 2-methyl propan-1-ol at 298.15 K have been measured over the entire composition range. All mixed endothermically with the maximum values ofH ^E occurring at equimole fraction. Comments about the molecular interactions contributing to the excess enthalpies of a cyclic ketone + an alcohol are made on the basis of these results.     

An indirect method for the spectrofluorimetric determination of trace amounts of germanium after extraction as an ion association complex with rhodamine B in the presence of chromotropic acid

A highly sensitive and selective spectrofluorimetric method for the determination of 0.05-2.00 mug germanium is described. Germanium is treated with chromotropic acid at pH 2.5 and the resultant anionic complex is extracted as an ion pair with rhodamine into toluene. Addition of butanol to the organic extract releases the fluorescent dye and facilitates its measurement at 570 nm after exciting at 540 nm. The method provides a detection limit of 0.003 mug ml(-1) and is virtually free from interference from extraneous ions. The relative standard deviaiton is 2.9% for ten determinations of 1.0 mug germanium. The method has been applied to the determination of germanium in various ores, minerals and rock samples.     

Total synthesis of d-(+)-biotin

A total synthesis of d-(+)-biotin is described starting from d-(+)-glucosamine using acyliminium chemistry.     

Studies on polymerization of vinyl acetate using ylide as an initiator and degradative transfer agent

Polymerization of vinyl acetate initiated by β-picolinium p-chlorophenacylide was carried out at 30, 35, and 40°C, using conventional dilatometric technique. The initiator and the monomer exponent values were 0.80 ± 0.15 and unity, respectively. The polymerization was inhibited in the presence of hydroquinone, but was favored by nonpolar solvent and polymerization temperature. The energy of activation was 90.3 KJ mol^?1. An average value of k/k_t for the present system was found to be 0.37 × 10^?2. The results are explained in terms of a radical mode of polymerization with degradative initiator transfer; the principal mode of termination, however, was bimolecular.