X-ray photoelectron spectra and Auger studies of the surface oxidation of cobalt

Surface oxidation of Co has been investigated at different temperatures in the 300–600 K range at oxygen exposures upto 106 L by XPES and AES techniques. In the XPES, both the valence band and core level bands have been employed to monitor the oxidation while in the AES, metal Auger intensity ratios as well as O(KLL)/Co(L23M45M45) ratios have been examined. Only CoO is formed on the surface at high oxygen exposures at and above 500 K.

Proton NMR studies of dihalogenated phenyl benzamides: two-dimensional higher quantum methodologies

The scalar coupled proton NMR spectra of many organic molecules possessing more than one phenyl ring are generally complex due to degeneracy of transitions arising from the closely resonating protons, in addition to several short- and long- range couplings experienced by each proton. Analogous situations are generally encountered in derivatives of halogenated benzanilides. Extraction of information from such spectra is challenging and demands the differentiation of spectrum pertaining to each phenyl ring and the simplification of their spectral complexity. The present study employs the blend of independent spin system filtering and the spin-state selective detection of single quantum (SO) transitions by the two-dimensional multiple quantum (MQ) methodology in achieving this goal. The precise values of the scalar couplings of very small magnitudes have been derived by double quantum resolved experiments. The experiments also provide the relative signs of heteronuclear couplings. Studies on four isomers of dilhalogenated benzanilides are reported in this work.

Electron- Spin-Resonance studies of phase transitions in double propionates

Detailed ESR investigations of Mn2+ substituting for Ca2+ in Ca2Sr(C2H5COO)6, (DSP) and Ca2Pb(C2H5COO)6, (DLP) and Ca2Ba(C2H5COO)6, (DBP), in single crystals and powders, over the temperature range from 300°C to -180°C have been carried out to study the successive phase transitions in these compounds. Spectra have been analyzed in terms of axial spin Hamiltonians and the temperature dependences of the parameters studied. Across the I-II transition, new physically and chemically inequivalent sites appear indicating the disappearance of the diad axes on which the propionate groups are located, bringing out the connection between the motional states of the propionate groups and the occurrence of ferroelectricity. The II-III transition also causes chemically inequivalent sites to develop, indicating that the transitions may not be isomorphous as believed previously. Similarities and dissimilarities of the ESR spectra of DLP, DSP and DBP are discussed in relation to the phase transitions.

Kinetic studies of the reactions of hexachlorocyclotriphosphazene and octachlorocyclotetraphosphazene with t-butylamine

The rates of the reactions of hexachlorocyclotriphosphazene (N3P3Cl6) and octachlorocyclotetraphosphazene (N4P4Cl8) with t-butylamine in methyl cyanide were determined at three temperatures in the range 273–308 K. The reaction of N3P3Cl6 was also studied in tetrahydrofuran. Rigorous purification of the chlorophosphazenes and the solvents was essential to obtain reproducible results. An SN2(P) mechanism involving the formation of a five-co-ordinate phosphorus intermediate is in accord with the kinetic data. The greater reactivity of N4P4Cl8 compared to that of N3P3Cl6 arises entirely from the lowering of the enthalpy of activation. The effects of ring size and the solvent on the rates are discussed in terms of the activation parameters.

ESR studies of phase transitions in double propionates

Detailed ESR investigations of Mn2+ substituting for Ca2+ in Ca2Sr(C2H5COO)6 (DSP), Ca2Pb(C2H5COO)6 (DLP) and Ca2Ba(C2H5COO)6 (DBP), in single crystals and powders, over the temperature range from 200°C to -180°C have been carried out to study the successive phase transitions in these compounds. (DSP: [Tetragonal] ← 8.5°C → [tetragonal, ferroelectric] [tetragonal] ← -169°C → [monoclinic, ferroelectric]; DLP : [tetragonal] ← 60°C → [tetragonal, ferroelectric] ← -71.5°C → [monoclinic, ferroelectric]; [Cubic] ← -6°C → [orthorhombic] ← -75°C → [?]). Spectra have been analysed in terms of axial spin Hamiltonians and the temperature dependences of the parameters studied. In DSP and DLP across the I ↔ II transition, new physically and chemically inequivalent sites appear indicating the disappearance of the diad axes on which the propionate groups are located, bringing out the connection between the motional states of the propionate groups and the occurence of ferroelectricity. The II ↔ III transition also causes chemically inequivalent sites to develop, indicating that the transitions may not be isomorphous as believed previously. In DBP, the -6°C transition leads to (i) a doubling of both physically and chemically inequivalent sites (ii) a small (150 G at -6°C to 170 G at -8°C), but abrupt change in the magnitude of the zero-field splitting tensor D, and (iii) displacements of the orientations of the D tensors. Results are interpreted in terms of alternate rotations of the oxygen octahedra, showing participation of the carboxyl oxygens in the transition. No drastic changes in the parameters occur across the -75°C transition consistent with its second order nature. Similarities and dissimilarities of the ESR spectra of the three compounds in relation to the phase transitions, are discussed.

Studies on diglycine sulphate

Both diglycine sulphate (DGS) and diglycine sulphate monohydrate (DGS.H2O) are reported to crystallize from solution with pH < 1(1,2). DGS.H2O (point group 2/m; Z = 4) shows a dielectric anomaly at 72°C suggestive of antiferroelectric transition(1). The crystals obtained by us from solution with pH < 0.5 at 20-25°C were always DGS (point group mmm; Z = 8) as confirmed by X-ray studies. The measurement of its dielectric constant along [100], [010] and [001] did not indicate any phase transition in the range 5-400°K. Thus DGS is a normal dielectric unlike TGS. The polarized Raman spectra and the infrared spectra were recorded to examine the configuration of glycine in DGS(3). The vibration spectra reveals that both the glycines in DGS exist as NH3+CH2COOH, thus precluding the hydrogen bond of the type N+-H…O- which exists between two glycine units in TGS. This seems to be a good reason for the difference in the dielectric behaviour of these two glycine sulphates.

Fluorescent probe and NMR studies of the aggregation of bile salts in aqueous solution

The binding of the fluorescent probes 1-anilino-8-naphthalene sulfonate and dansyl cadaverine to the sodium salts of cholic, deoxycholic and dehydrocholic acids has been investigated. Enhanced probe solubilisation accompanies aggregation. Monitoring of fluorescence intensities as a function of bile salt concentration permits the detection of primary micelle formation, as well as secondary association. The transition concentrations obtained by fluorescence are in good agreement with values determined for the critical micelle concentrations, by other methods. Differences in the behaviour of cholate and deoxycholate have been noted. Fluorescence polarisation studies of 1,6-diphenyl-1,3,5-hexatriene solubilised in bile salt micelles suggest a higher microviscosity for the interior of the deoxycholate micelle as compared to cholate. 1H NMR studies of deoxycholate over the range 1–100 mg/ml suggest that micelle formation leads to a greater immobilisation of the C18 and C19 methyl groups as compared to the C21 methyl group. Well resolved 13C resonances are observed for all three steroids even at high concentration. Both fluorescence and NMR studies confirm that dehydrocholate does not aggregate.

EPR studies on donor doped BaTiO3 grain boundary layer ceramic dielectrics

Donor doped BaTiO3 ceramics become insulating5 under controlled conditions with effective dielectric constants >10. The changes in EPR signals indicate that a certain fraction of the donor doped BaTiO3 is cubic even at room temperature and that the cubic fraction increases with the donor content. X-ray powder diffraction data support the EPR results. The coexistence of both the phases over a range of temperature is characteristic of diffused phase transition. The effect of grain size variation on EPR signal intensities indicate that the boundary layers surrounding the grains may constitute the cubic phase as a result of higher Ba-vacancies and donor contents at the grain boundary layer than in the bulk. Since the acceptor states arising from the Ba-vacancies and the impurities are activated in the cubic phase, they capture electrons from the conduction band, rendering the cubic phase electrically more insulating than the semiconductive tetragonal grain interiors. Thus, the cubic grain boundary layers act as effective dielectric media where the field tends to concentrate.

Infrared studies on the conformation of synthetic alamethicin fragments and model peptides containing .alpha.-aminoisobutyric acid

ABSTRACT: Infrared studies of synthetic alamethicin fragments and model peptides containing a-aminoisobutyric acid (Aib) have been carried out in solution. Tripeptides and larger fragments exhibit a strong tendency to form /3 turns, stabilized by 4 - 1 10-atom hydrogen bonds. Dipeptides show less well-defined structures, though C5 and C7 conformations are detectable. Conformational restrictions imposed by Aib residues result in these peptides populating a limited range of states. Integrated intensities of the hydrogen-bonded N-H stretching band can be used to quantitate the number of intramolecular hydrogen bonds. Predictions made from infrared data are in excellent agreement with nuclear magnetic resonance and X-ray diffraction studies. Assignments of the urethane and tertiary amide carbonyl groups in the free state have been made in model peptides. Shifts to lower frequency on hydrogen bonding are observed for the carbonyl groups. The 1-6 segment of alamethicin is shown to adopt a 310 helical structure stabilized by four intramolecular hydrogen bonds. The fragments Boc-Leu-Aib-Pro-Val-Aib-OMe (1 2-1 6) and Boc-Gly-Leu-Aib-Pro-Val-Aib-OMe (1 1-1 6) possess structures involving 4 - 1 and 5 - 1 hydrogen bonds. Supporting evidence for these structures is obtained from proton nuclear magnetic resonance studies.

Ignition delay studies on hydrocarbon fuel with and without additives

Single pulse shock tube facility has been developed in the High Temperature Chemical Kinetics Lab, Aerospace Engineering Department, to carry out ignition delay studies and spectroscopic investigations of hydrocarbon fuels. Our main emphasis is on measuring ignition delay through pressure rise and by monitoring CH emission for various jet fuels and finding suitable additives for reducing the delay. Initially the shock tube was tested and calibrated by measuring the ignition delay of C2H6-O2 mixture. The results are in good agreement with earlier published works. Ignition times of exo-tetrahdyrodicyclopentadiene (C10H16), which is a leading candidate fuel for scramjet propulsion has been studied in the reflected shock region in the temperature range 1250 - 1750 K with and without adding Triethylamine (TEA). Addition of TEA results in substantial reduction of ignition delay of C10H16.

Studies on Aspergillus niger glutamine synthetase: Regulation of enzyme levels by nitrogen sources and identification of active site residues

The specific activity of glutamine synthetase (L-glutamate: ammonia ligase, EC 6.3.1.2) in surface grown Aspergillus niger was increased 3-5 fold when grown on L-glutamate or potassium nitrate, compared to the activity obtained on ammonium chloride. The levels of glutamine synthetase was regulated by the availability of nitrogen source like NH4 + , and further, the enzyme is repressed by increasing concentrations of NH4 +. In contrast to other micro-organisms, the Aspergillus niger enzyme was neither specifically inactivated by NH4+ or L-glutamine nor regulated by covalent modification.Glutamine synthetase from Aspergillus niger was purified to homogenity. The native enzyme is octameric with a molecular weight of 385,000±25,000. The enzyme also catalyses Mn2+ or Mg2+-dependent synthetase and Mn2+-dependent transferase activity.Aspergillus niger glutamine synthetase was completely inactivated by two mol of phenylglyoxal and one mol of N-ethylmaleimide with second order rate constants of 3·8 M–1 min–1 and 760 M–1 min–1 respectively. Ligands like Mg. ATP, Mg. ADP, Mg. AMP, L-glutamate NH4+, Mn2+ protected the enzyme against inactivation. The pattern of inactivation and protection afforded by different ligands against N-ethylamaleimide and phenylglyoxal was remarkably similar. These results suggest that metal ATP complex acts as a substrate and interacts with an arginine ressidue at the active site. Further, the metal ion and the free nucleotide probably interact at other sites on the enzyme affecting the catalytic activity.

Studies on diglycine sulphate

The dielectric measurements on diglycine sulphate in the temperature range 5-400 K, show that it is a normal dielectric, unlike triglycine sulphate which is a ferroelectric. The difference in the dielectric behavior of these two glycine sulphates has been explained on the basis of certain structural features derived from a study of their vibration spectra.

Surface Discharge Studies with Uniform Field Electrodes at Low Pressures

An investigation of power frequency (50 Hz) surface partial discharges in dry air, using 21r/3 Rogowski profile electrodes in the low pressure range of 0.067 to 91.333 kPa, shows that for the discharges occurring symmetrically around the electrodes and just outside the uniform field region, the breakdown voltages are 20 to 30% lower than those accounted for by the usual Paschen values. Emphasis, therefore, has been given to modified values of breakdown voltages for any useful calculations. The effect of reduced pressure on inception voltage has been discussed and an attempt has been made to explain the difference between the observed and calculated values on the basis of a pressure-dependent secondary ionization coefficient. It is shown that increasing the insulation thickness in a critical pressure range (0.067 to 0.400 kPa) does not allow any significant increase in the discharge free working stress of the insulation system. At higher pressures (>0.400 kPa) the increase in inception voltage with thickness and pressure follows an equation which is expected to hold for other insulating materials as well.

Role of Capping Ligands on the Nanoparticles in the Modulation of Properties of a Hybrid Matrix of Nanoparticles in a 2D Film and in a Supramolecular Organogel

We incorporate various gold nanoparticles (AuNPs) capped with different ligands in two-dimensional films and three-dimensional aggregates derived from N-stearoyl-L-alanine and N-lauroyl-L-alanine, respectively. The assemblies of N-stearoyl-L-alanine afforded stable films at the air-water interface. More compact assemblies were formed upon incorporation of AuNPs in the air-water interface of N-stearoyl-L-alanine. We then examined the effects of incorporation of various AuNPs functionalized with different capping ligands in three-dimensional assemblies of N-lauroyl-L-alanine, a compound that formed a gel in hydrocarbons. The profound influence of nanoparticle incorporation into physical gels was evident from evaluation of various microscopic and bulk properties. The interaction of AuNPs with the gelator assembly was found to depend critically on the capping ligands protecting the Au surface of the gold nanoparticles. Transmission electron microscopy (TEM) showed a long-range directional assembly of certain AuNPs along the gel fibers. Scanning electron microscopy (SEM) images of the freeze-dried gels and nanocomposites indicate that the morphological transformation in the composite microstructures depends significantly on the capping agent of the nanoparticles. Differential scanning calorimetry (DSC) showed that gel formation from sol occurred at a lower temperature upon incorporation of AuNPs having capping ligands that were able to align and noncovalently interact with the gel fibers. Rheological studies indicate that the gel-nanoparticle composites exhibit significantly greater viscoelasticity compared to the native gel alone when the capping ligands are able to interact through interdigitation into the gelator assembly. Thus, it was possible to define a clear relationship between the materials and the molecular-level properties by means of manipulation of the information inscribed on the NP surface.

Interactions of aromatic mannosyl disulfide derivatives with Concanavalin A: synthesis, thermodynamic and NMR spectroscopy studies

α-d-Mannopyranosyl units were attached to an aromatic scaffold through disulfide linkages to obtain mono- to trivalent glycosylated ligands for lectin binding studies. Isothermal titration calorimetric (ITC) measurements indicated that binding affinities of these derivatives to Concanavalin A (Con A) were comparable to or slightly higher than that of methyl α-d-mannopyranoside (Ka values in the range of 104 M−1). The stoichiometries of the lectin-ligand complexes were in agreement with the formal valencies (1–3) of the respective ligands indicating cross-linking in interactions with the di- and trivalent derivatives. Multivalency effects could not, however, be observed with the latter. These ligands were shown to bind to the carbohydrate binding site of Con A using saturation transfer difference (STD) NMR competition experiments.