New modifications in 15 UD pelletron at nuclear science centre

The 15 UD pelletron at NSC has been operational and performed well during the last 11 years. There have been major modifications performed for upgradation of pelletron system over this period. Major upgradations which have been implemented are new resistor network system for voltage gradient, doublet to singlet unit conversion for accelerator units, turbopump based gas stripper system etc. In addition accelerator mass spectroscopy program has also been started. A new multi-cathode source, Wien filter etc. have been procured and will be added soon in the system. An overview of the most significant upgradations undertaken and other activities for the system are being reported in the present paper.     

Characterization of the tryptophan residues of human placental ribonuclease inhibitor and its complex with bovine pancreatic ribonuclease A by steady-state and time-resolved emission spectroscopy

Human placental ribonuclease inhibitor (hRI) containing six tryptophan (Trp) residues located at positions 19, 261, 263, 318, 375, and 438 and its complex with RNase A have been studied using steady-state and time-resolved fluorescence (298 K) as well as low-temperature phosphorescence (77 K). Two Trp residues in wild-type hRI and also in the protein-protein complex with RNase A are resolved optically. The accessible surface area values of Trp residues in the wild-type hRI and its complex and consideration of inter-Trp energy transfer in the wild-type hRI reveal that one of the Trp residues is Trp19, which is located in a hydrophobic buried region. The other Trp residue is tentatively assigned as Trp375 based on experimental results on wild-type hRI and its complex. This residue in the wild-type hRI is more or less solvent exposed. Both the Trp residues are perturbed slightly on complex formation. Trp19 moves slightly toward a more hydrophobic region, and the environment of Trp375 becomes less solvent exposed. The complex formation also results in a more heterogeneous environment for both the optically resolved Trp residues.     

Temperature variation of DC conductivity of poly(3-alkyl thiophenes) and their cocrystals

The dc conductivity of poly(3-alkyl thiophenes) (P3ATs) and their cocrystals are measured in the temperature range of -130 to 150 degrees C. Both solvent-cast films and the melt-cooled films are used. The former exhibit a sharp increase followed by a decrease in conductivity, whereas the latter show only a sigmoidal increase in conductivity with temperature. The sigmoidal increase of the melt-cooled samples is dependent on the regioregularity and alkyl chain length of the samples and is explained from the solid-state transformation of the interdigited type-II crystal to a noninterdigited type-I crystal. The type-I crystal itself has lower conductivity than type-II crystals, and the samples exhibit a blue shift in UV-vis absorption spectra with an increase in temperature. So the sigmoidal increase of conductivity is attributed to the increase in carrier mobility with temperature in the type-I crystals. The X-ray and DSC results suggest that during the transformation of type-II to type-I crystals with increasing temperature, localized crystallites of smaller dimensions separated by narrower amorphous portions are produced throughout the whole matrix. But in the type-II polymorph, the crystallites are large with a wider gap in between. The sigmoidal increase is attributed to the easier hopping of the charge carrier among the localized crystallites of the type-I crystal with increasing temperature. In the cocrystals, the smaller sigmoidal increase with increasing irregular sample concentration is valid for a lower concentration of such localized crystallites. The same is true for cocrystals with longer alkyl chain lengths. The interfibrillar contribution of conductivity through the network junctions together with the carrier hopping between the localized crystallites might be a possible reason for the metallic-type behavior of solvent-cast samples after a certain temperature. The melt-cooled films do not exhibit metallic-type behavior because of the absence of a fibrillar network morphology.     

Vibrational coupling in carboxylic acid dimers

The vibrational level splitting in the ground electronic state of carboxylic acid dimers mediated by the doubly hydrogen-bonded networks are investigated using pure and mixed dimers of benzoic acid with formic acid as molecular prototypes. Within the 0-2000-cm(-1) range, the frequencies for the fundamental and combination vibrations of the two dimers are experimentally measured by using dispersed fluorescence spectroscopy in a supersonic jet expansion. Density-functional-theory calculations predict that most of the dimer vibrations are essentially in-phase and out-of-phase combinations of the monomer modes, and many of such combinations show significantly large splitting in vibrational frequencies. The infrared spectrum of the jet-cooled benzoic acid dimer, reported recently by Bakker et al. [J. Chem. Phys. 119, 11180 (2003)], has been used along with the dispersed fluorescence spectra to analyze the coupled g-u vibrational levels. Assignments of the dispersed fluorescence spectra of the mixed dimer are suggested by comparing the vibronic features with those in the homodimer spectrum and the predictions of density-functional-theory calculation. The fluorescence spectra measured by excitations of the low-lying single vibronic levels of the mixed dimer reveal that the hydrogen-bond vibrations are extensively mixed with the ring modes in the S1 surface.     

Enhanced photoluminescence properties of Gd (x-1) Sr x O: CdO nanocores and their study of optical,structural, and morphological characteristics

Synthesis of Gd doped Sr_x O: CdO (x = 1.4, 1.6, 1.8) nanostructures (NS) was achieved through the coprecipitation method by using CTAB (cetyl trimethyl ammonium bromide) with the purpose to investigate the effect of Gd doping on the optical, structural, morphological, and photoluminescence properties at room temperature. Mixed phase of tetragonal crystal structure verified via X-ray diffraction technique, no structural variation was observed except lattice distortion. Size of the crystallites (D), morphology studied by SEM (scanning electron microscopy) analysis, nanoparticles (NPs) crystalized roughly flake-like morphology with homogeneous particle distribution centered at ~ 78 nm, ~56 nm, ~65 nm, ~88 nm for pure and Gd _(x-1) doped Sr _xO: CdO nanostructure, respectively. Fourier transform infrared spectroscopic investigation (FTIR) revealed the presence of Gd–O–Gd, Cd–O, Sr–O, and OH peaks appeared at ~1321 cm ^?1, ~1550 cm ^?1, ~1400 cm ^?1–3300 cm ^?1 with small variation in vibration modes due to Gd doping. Optical absorptivity observed in the range of 325 nm–359 nm (redshifted) with absorption edges at 346 nm, 364 nm, and 380 nm for Gd _(x-1) doped Sr _xO: CdO nanostructure, respectively. This redshift on the bandgap was discussed in terms of new band levels below conduction band. The energy gap was calculated using Kubelka-Munk theory and was found to be in the range of 3.22 eV–2.61 eV. X-ray photoelectron spectroscopy (XPS) performed to determine chemical composition and binding energies of Gd 3d _3/2, Sr 3d _3/2, and Cd 3d _3/2, O1s, and C1s observed at 150.8 eV, 141.6 eV, 411.0 eV, 530.4 eV, and 285.6 eV indicating Gd⁺³ ion replaces Sr⁺² in all concentrations. Our results showed that Gd-doped Sr _xO: CdO nanoparticles exhibited enhanced photoluminescence (PL) properties in contrast to the pure Gd₂O₃ with Gd⁺³ randomly incorporated into crystal structure, probably in tetrahedral sites. The composition of Gd _0.6 doped Sr _x O: CdO NS exhibited photoluminescent emission spectra, peaks centered at 433 ± 3 nm, 449 ± 3 nm, and 469 ± 2 nm (λ _excitation = 318 nm) and for Gd _0.8 doped Sr _x O: CdO nanostructure showed broad emission peak at 412 ± 2 nm to 433 ± 2 nm (λ _excitation = 380 nm), which indicates a reduction in defects with an increase in Gd doping. The transitions can be ascertained with shielding of 4f shells of Gd ⁺³ ions by 6s, 5d shells by the interaction of other Gd ⁺³ ions.     

Origin of methyl torsional barrier in 1-methyl-2-(1H)-pyridone

The laser induced fluorescence excitation and single vibronic excitation dispersed fluorescence spectra have been studied for supersonic jet cooled 1-methyl-2(1h)-pyridone. The methyl torsional bands and some low frequency vibrational transitions were assigned for both ground and excited states. The torsional parameters V(3)=244 cm(-1) and V(6)=15 cm(-1) for the ground state and V(3)=164 cm(-1) and V(6)=40 cm(-1) for the excited state were obtained. To get the insight into the methyl torsional barrier, ab initio calculations were performed and compared with the experimental results. Origin of potential barrier was traced by partitioning the barrier energy into changes in bond-antibond interaction, structural, and steric energies accompanying methyl rotation using natural bond orbital analysis. The role of local interactions in ascertaining the barrier potential reveals that its nature cannot be understood without considering the molecular flexing. The hyperconjugation between CHsigma(*) and ring pi(*) observed in lowest unoccupied molecular orbital (LUMO) stabilizes the methyl group conformer that undergoes a 60 degrees rotation in the excited state with respect to that of the ground state, and it is the change in LUMO that plays important role in the excited state barrier formation.     

Asymmetric reductive ring-opening of bicyclic olefins catalyzed by palladium and nickel complexes

[reaction: see text] Asymmetric reductive ring opening of oxa- and azabenzonorbornadienes with organic acids and zinc powder under mild conditions catalyzed by Ni(binap)Cl(2) or Pd(binap)I(2) produces the corresponding 1,2-dihydronaphth-1-ols in good to excellent yields with high enantioselectivity.     

Ionic and dipolar solvation dynamics in liquid water

The solvation time correlation function for solvation in liquid water was measured recently. The solvation was found to be very fast, with a time constant equal to 55 fs. In this article we present theoretical studies on solvation dynamics of ionic and dipolar solutes in liquid water, based on the molecular hydrodynamic approach developed earlier. The molecular hydrodynamic theory can successfully predict the ultrafast dynamics of solvation in liquid water as observed from recent experiments. The present study also reveals some interesting aspects of dipolar solvation dynamics, which differs significantly from that of ionic solvation. Dedicated to Prof. C N R Rao on his 60th birthday