990 resultados para 7137-106
Resumo:
Exchange of energy between Zeeman and dipolar reservoirs in the rotating frame during spin-lock has important implications for the understanding of the Hartmann-Hahn cross polarisation process and is examined here with experiments on ammonium dihydrogen phosphate. It is observed that energy exchange between the two reservoirs takes place indicating that the relative magnitude of the dipolar coupling in relation to the applied r.f. field may have a role to play in determining the rate of exchange of energy between the two reservoirs.
Resumo:
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.
Resumo:
The unsymmetrical diphosphazanes X2PN(Pr(i))PYY'(1a-1h) {X = Ph, YY' = O2 C6H4 (1a) or YY' = O2C12H8 (1b); X = Ph, Y = Ph, Y' = OC6H4Me-4 (1c), OC6H4Br-4 (1d), OC6H3Me2-3,5 (1e), OC5H4N-2 (1f), N2C3HMe2-3,5 (1g) or Cl (1h)} react with [M(CO)4(NHC5H10)2] (M = Mo, W) to yield the cis-chelate complexes [M(CO)4{X2PN(Pr(i)) PYY'}] {M = Mo (2a-2h); M = W (3-f,3-g)}. These complexes have been characterized by H-1, P-31 and C-13 NMR and IR spectroscopic studies.
Resumo:
We study the electronic structure of NaCuO2 by analysing experimental core level photoemission and X-ray absorption spectra using a cluster as well as an Anderson impurity Hamiltonian including the band structure of the oxygen sublattice. We show that the X-ray absorption results unambiguously establish a negative value of the charge transfer energy, A. Further, mean-field calculations for the edge-shared one-dimensional CuO2 lattice of NaCuO2 within the multiband Hubbard Hamiltonian show that the origin of the insulating nature lies in the band structure rather than in the correlation effects. LMTO-ASA band structure calculations suggest that NaCuO2 is an insulator with a gap of around 1 eV.
Resumo:
A versatile fungus isolated in our laboratory and identified as Mucor piriformis has been shown to effect novel and preparatively useful transformations in steroids and morphine alkaloids. The organism very effectively carries out hydroxylation of various C-19 and C-21 steroids at 7 and 14-positions. Although the organism is capable of catalysing hydroxylation at 6 beta and 11 alpha-positions, these are not the major activities. The 14 alpha-hydroxylase appears to have a broad substrate specificity. However, steroids with a bulky substitution at C-17 alpha-position or without the 4-en-3-one group are not accepted as substrates by the 14 alpha-hydroxylase system. Studies have demonstrated how various C-19 and C-21 steroids can be modified to yield new structures which are either difficult to prepare by traditional methods or hitherto unknown. The organism also very efficiently and selectively carries out the N-dealkylation of thebaine and its N-variants. Interestingly, the nor-compound formed does not get further metabolized. Since thebaine is very often used as a starting material to synthesize various morphine agonists as well as antagonists, and one of the steps involved in their preparation is the N-dealkylation reaction, the microbial process could certainly offer an alternative approach.
Resumo:
The chemical modifications of structure, reactivity and catalytic properties of layered triple perovskite oxides, related to the YBa2Cu3O7-delta (123) system, have been briefly reviewed. These oxides form a versatile family of materials with wide-ranging chemical and physical properties. The multiple sites available for chemical doping, and the ability to reversibly intercalate oxygen at the defect sites have rendered these oxides important model systems in the area of oxide catalysis. An attempt has been made to comprehend the hitherto known catalytic reactions and correlate them to various factors like structure, oxygen diffusional limitations, different geometries adopted by various substituents, oxidative non-stoichiometry and activation energy for oxygen desorption. In particular, results on the enhanced catalytic activity of cobalt-substituted 123 oxide systems towards the selective catalytic oxidation of ammonia to nitric oxide and carbon monoxide to carbon dioxide are presented.
Resumo:
We describe three different families of metal oxides, viz., (i) protonated layered perovskites, (ii) framework phosphates of NASICON and KTiOPO4 (KTP) structures and (iii) layered and three-dimensional oxides in the H-V-W-O system, synthesized by 'soft-chemical' routes involving respectively ion-exchange, redox deinteracalation and acid-leaching from appropriate parent oxides. Oxides of the first family, HyA2B3O10(A = La/Ca; B = Ti/Nb), exhibit variable Bronsted acidity and intercalation behaviour that depend on the interlayer structure. V2(PO4)3 prepared by oxidative deintercalation from Na3V2(PO4)3 is a new host material exhibiting reductive insertion of lithium/hydrogen, while K0.5Nb0.5 M0.5OPO4(M = Ti, V) are novel KTP-like materials exhibiting second harmonic generation of 1064 nm radiation. HxVxW1-xO3 for x = 0.125 and 0.33 possessing alpha-MoO3 and hexagonal WO3 structures, prepared by acid-leaching of LiVWO6, represent functionalized oxide materials exhibiting redox and acid-base intercalation reactivity.
Resumo:
Star formation properties in Giant Extragalactic H II Regions (GEHRs) are investigated using optical photometry and evolutionary population synthesis models. Photometric data in $BVR$ bands and in the emission line of H-alpha are obtained by CCD imaging at Vainu Bappu Observatory, Kavalur. Aperture photometry is performed for 180 GEHRs in galaxies NGC 1365, 1566, 2366, 2903, 2997, 3351, 4303, 4449, 4656 and 5253. Thirty six of these GEHRs having published spectroscopic data are studied for star formation properties. The population synthesis model is constructed based on Maeder's stellar evolutionary and Kurucz stellar atmosphere models, to synthesize observational quantities of embedded clusters in GEHRs. The observed H-alpha luminosity is a measure of the number of massive stars while the contribution to BVR bands is from intermediate mass (5-15 solar mass) stars when the cluster is young and from evolving supergiants when the cluster is old (age >/= 6~Myr). Differential reddening between gas and embedded stars is essential to constrain the dereddened cluster colors within the range of youngest clusters. Obscuring dust closely associated with gas, which is distributed in filaments and clumps, as in the case of 30 Doradus, is the most likely configuration giving rise to net reduction of extinction towards stars. The fraction of the stellar photons escaping the nebula unattenuated is estimated to be 50%. GEHRs are rarely found to be simple systems containing stars from single generation. In the present sample such regions in addition to being older than 3~Myr, have their Lyman continuum luminosity reduced by as much as 60%, compared to the observed $B$ band luminosity for a normal IMF. The missing ionizing photons may be escaping the nebula, leading to the ionization of extra-H II region ionized medium. Co-existence of young (age = 5 Myr; stars producing ionizing photons) and old populations (~10~Myr; Red Supergiants) is found to be common in GEHRs. The emission and continuum knots are seen spatially separated (40-100 pc) on CCD images in NGC 2997, 4303 and 4449 and may be direct evidences for the co-existence of young and old populations in giant star forming complexes. Triggering of star formation from earlier bursts is the most likely cause of new generation of stars, and may be a common phenomenon in GEHRs. Spatial separation between the young and old stars (~30 pc) had been earlier reported in 30 Doradus. Thus GEHRs in nearby galaxies share many of the properties shown by 30 Dor, the nearest GEHR. (SECTION: Dissertation Summaries)
Resumo:
A simplified analysis is employed to handle a class of singular integro-differential equations for their solutions