Photodissociation dynamics of CH2ICl at 222, 236, 266, 280, and-304 nm

Dynamics of I*(P-2(1/2)) formation from CH2ICl dissociation has-been investigated at five different ultraviolet excitation wavelengths, e.g., 222, 236, 266, 280, and similar to304 nm. The quantum yield of I*((2)p(1/2)) production, phi*, has been measured by monitoring nascent I(P-2(3/2)) and I* concentrations using a resonance enhanced multiphoton ionization detection scheme. The measured quantum yield as a function of excitation energy follows the same trend as that of methyl iodide except at 236 run. The photodissociation dynamics of CH2ICl also involves three upper states similar to methyl iodide, and a qualitative correlation diagram has been constructed to account for the observed quantum yield. From the difference in behavior at 236 nm, it appears that the crossing region between the two excited states ((3)Q(0) and (1)Q(1)) is located near the exit valley away from the Franck Condon excitation region. The B- and C-band transitions do not participate in the dynamics, and the perturbation of the methyl iodide states due to Cl-I interaction is relatively weak at the photolysis wavelengths employed in this investigation.

High-Temperature Phase Transition Studies in a Novel Fast Ion Conductor, Na2Cd(SO4)2, Probed by Raman Spectroscopy

Temperature-dependent Raman spectroscopic studies were carried out on Na2Cd(SO4)(2) from room temperature to 600 degrees C. We observe two transitions at around 280 and 565 degrees C. These transitions are driven by the change in the SO4 ion. On the basis of these studies, one can explain the changes in the conductivity data observed around 280 and 565 degrees C. At 280 degrees C, spontaneous tilting of the SO4 ion leads to restriction of Na+ mobility. Above 565 degrees C, the SO4 ion starts to rotate freely, leading to increased mobility of Na+ ion in the channel.

Thermal Degradation Processes in Poly(xylylene sulfides) Investigated by Comparative Direct Pyrolysis MS and Flash Pyrolysis GC/MS Experiments

The thermal degradation processes of two sulfur polymers, poly(xylylene sulfide) (PXM) and poly(xylylene disulfide) (PXD), were investigated in parallel by direct pyrolysis mass spectrometry (DPMS) and flash pyrolysis GC/MS (Py-GC/MS). Thermogravimetric data showed that these polymers decompose with two separate steps in the temperature ranges of 250-280 and 600-650 degrees C, leaving a high amount of residue (about 50% at 800 degrees C). The pyrolysis products detected by DPMS in the first degradation step of PXM and PXD were terminated by three types of end groups, -CH3, -CH2SH, and -CH=S, originating from thermal cleavage reactions involving a series of homolytic chain scissions followed by hydrogen transfer reactions, generating several oligomers containing some intact xylylene sulfide repeating units. The presence of pyrolysis compounds containing some stilbene-like units in the first degradation step has also been observed. Their formation has been accounted for with a parallel cleavage involving the elimination of H2S from the PXM main chains. These unsaturated units can undergo cross-linking at higher temperatures, producing the high amount of char residue observed. The thermal degradation compounds detected by DPMS in the second decomposition step at about 600-650 degrees C were constituted of condensed aromatic molecules containing dihydrofenanthrene and fenanthrene units. These compounds might be generated from the polymer chains containing stilbene units, by isomerization and dehydrogenation reactions. The pyrolysis products obtained in the Py-GC/MS of PXM and PXD at 610 degrees C are almost identical. The relative abundance in the pyrolysate and the spectral properties of the main pyrolysis products were found to be in generally good agreement with those obtained by DPMS. Polycyclic aromatic hydrocarbons (PAHs) were also detected by Py-GC/MS but in minor amounts with respect to DPMS. This apparent discrepancy was due to the simultaneous detection of PAHs together with all pyrolysis products in the Py-GC/MS, whereas in DPMS they were detected in the second thermal degradation step without the greatest part of pyrolysis compounds generated in the first degradation step. The results obtained by DPMS and PSI-GC/MS experiments showed complementary data for the degradation of PXM and PXD and, therefore, allowed the unequivocal formulation of the thermal degradation mechanism for these sulfur-containing polymers.

Disulfide luminescence. Emission characteristics of cyclic tetrapeptide disulfides

Luminescence has been detected in cyclic tetrapeptide disulfides containing only nonaromatic residues. Excitation of the S-S- n-cr transition between 280 and 290 nm leads to.ernission in the region 300-340 nm. The position and intensity of the emission band depends on the stereochemistry of the peptide and polarity of the solvent. Quantum yields ranging from 0.002 to 0.026 have been determined. Disulfide luminescence is quenched by oxygen and enhanced in solutions saturated with nitrogen. Contributions from disulfide linkages should be considered, when analysing the emission spectra of proteins, lacking tryptophan but having a high cystine content.

NMR studies of molecular dynamics in tetramethylammonium tetrabromo cadmate

Internal motions in a A2BX4 compound (tetramethylammonium tetrabromo cadmate) have been investigated using proton spin—lattice relaxation time (T1) and second moment (M2) measurements in the temperature range 77 to 400 K. T1 measurements at three Larmor frequencies (10, 20 and 30 MHz) show isotropic tumbling of the tetramethylammonium group, random reorientation of methyl groups and spin—rotation interaction, and the corresponding parameters have been computed. The cw spectrum is narrow throughout the temperature range and shows side bands at the lowest temperature. This observation, along with the free-induction-decay behavior at these temperatures, is interpreted as the onset of a coherent motion, e.g. methyl group quantum tunnelling.

An NMR study of the interaction of cytosine arabinoside and lysozyme

Abstract is not available.

Structural studies of analgesics and their interactions .10. A hydrated 1-1 complex between niflumic acid and ethanolamine, c13h8f3n2o-2.c2h8no+.h2o.

Mr= 361.3, triclinic, P1, a = 6-239 (2), b=11.280(2), c=12-451(2)A, a=101.2 (1), B= 92.3 (1), 7=99.9(1)°, V=844.123 A3, Z=2, Dx= 1.42, D m = 1.42 (1) Mg m -3, n(Cu Ka) = 1.5418 ,A., g = 1-102 mm -1, F(000) = 376, T= 293 K. Final R = 0.064 for 2150 observed reflections. The niflumic acid anions consist essentially of three planar groupings, namely, two six-membered rings and a carboxylate group attached to one of them. The invariant common structural features observed in the crystal structures of fenamates, namely, the coplanarity of the carboxyl group and the six-membered ring bearing it, and the internal hydrogen bond between the carboxyl group and the imino N atom that bridges the two sixmembered rings, are retained in the complex. The amino N atom is gauche with respect to the terminal hydroxyl group in the ethanolamine cation. The complexation between the two molecules is achieved through ionic and hydrogen-bonded interactions involving the carboxylate group in niflumic acid.

Fluorescent labelling of strychnine: A novel approach for recognition of strychnine binding sites on neuronal membrane

trychnine was coupled to fluorescein isothiocyanate to mark strychnine binding sites in spinal cord of rat. Specific binding of strychnine could be demonstrated in synaptosomal fraction. Addition of glycine to the strychninised membrane led to a decrease in fluorescence indicating same receptor loci.

Rural energy consumption patterns - A field study

This paper is a condensed version of the final report of a detailed field study of rural energy consumption patterns in six villages located west of Bangalore in the dry belt of Karnataka State in India. The study was carried out in two phases; first, a pilot study of four villages and second, the detailed study of six villages, the populations of which varied from around 350 to about 950. The pilot survey ended in late 1976, and most of the data was collected for the main project in 1977. Processing of the collected data was completed in 1980. The aim was to carry out a census survey, rather than a sample study. Hence, considerable effort was expended in production of both a suitable questionnaire, ensuring that all respondents were contacted, and devising methods which would accurately reflect the actual energy use in various energy-utilising activities. In the end, 560 households out of 578 (97%) were surveyed. The following ranking was found for the various energy sources in order of average percentage contribution to the annual total energy requirement: firewood, 81·6%; human energy, 7·7%; animal energy, 2·7%; kerosene, 2·1%; electricity, 0·6% and all other sources (rice husks, agro-wastes, coal and diesel fuel), 5·3%. In other words commercial fuels made only a small contribution to the overall energy use. It should be noted that dung cakes are not burned in this region. The average energy use pattern, sector by sector, again on a percentage basis, was as follows: domestic, 88·3%; industry, 4·7%; agriculture, 4·3%; lighting, 2·2% and transport, 0·5%. The total annual per capita energy consumption was 12·6 ± 1·2 GJ, giving an average annual household consumption of around 78·6 GJ.

Oxidative extraction and ion-exchange of lithium in Li2MoO3: synthesis of Li2âxMoO3 and H2MoO3

It is shown that lithium can be oxidatively extracted from Li2MoO3 at room temperature using Br2 in CHCl3. The delithiated oxides, Li2â��xMoO3 (0 < x â�¤ 1.5) retain the parent ordered rocksalt structure. Complete removal of lithium from Li2MoO3 using Br2 in CH3CN results in a poorly crystalline MoO3 that transforms to the stable structure at 280�°C. Li2MoO3 undergoes topotactic ion-exchange in aqueous H2SO4 to yield a new protonated oxide, H2MoO3.

An eels study of water, methanol, formaldehyde and formic acid adsorbed on clean and oxygen-covered zinc(0001) surfaces

Water adsorbs molecularly on a clean Zn(0001) surface; on a surface covered with atomic oxygen, however, hydroxyl species is produced due to proton abstraction by the surface oxygen atoms. Methanol, molecularly adsorbed on a clean surface at 80 K, transforms to methoxy species above 110 K. On an atomic oxygen-covered surface, adsorbed methanol gives rise to methoxy species and water, the latter arising from proton abstraction. HCHO adsorbs molecularly at 80 K on both clean as well as oxygen-covered surfaces and polymerizes at higher temperatures. Formic acid does not adsorb on a clean Zn surface, but on an oxygen-covered surface gives rise to formate and hydroxyl species.

An NMR study of the interaction of cytosine arabinoside and lysozyme

Abstract is not available.

Rural energy consumption patterns - A field study

This paper is a condensed version of the final report of a detailed field study of rural energy consumption patterns in six villages located west of Bangalore in the dry belt of Karnataka State in India. The study was carried out in two phases; first, a pilot study of four villages and second, the detailed study of six villages, the populations of which varied from around 350 to about 950. The pilot survey ended in late 1976, and most of the data was collected for the main project in 1977. Processing of the collected data was completed in 1980. The aim was to carry out a census survey, rather than a sample study. Hence, considerable effort was expended in production of both a suitable questionnaire, ensuring that all respondents were contacted, and devising methods which would accurately reflect the actual energy use in various energy-utilising activities. In the end, 560 households out of 578 (97%) were surveyed. The following ranking was found for the various energy sources in order of average percentage contribution to the annual total energy requirement: firewood, 81A·6%; human energy, 7A·7%; animal energy, 2A·7%; kerosene, 2A·1%; electricity, 0A·6% and all other sources (rice husks, agro-wastes, coal and diesel fuel), 5A·3%. In other words commercial fuels made only a small contribution to the overall energy use. It should be noted that dung cakes are not burned in this region. The average energy use pattern, sector by sector, again on a percentage basis, was as follows: domestic, 88A·3%; industry, 4A·7%; agriculture, 4A·3%; lighting, 2A·2% and transport, 0A·5%. The total annual per capita energy consumption was 12A·6 A± 1A·2 GJ, giving an average annual household consumption of around 78A·6 GJ.

A Novel Approach to the Study of Surface Oxidation States and Oxidation of Transition Metals by Auger Electron Spectroscopy

L$_{23}$ M$_{45}$ M$_{45}$/L$_{23}$ M$_{23}$ M$_{45}$, L$_{23}$ M$_{45}$ M$_{45}$/L$_{23}$ M$_{23}$ M$_{23}$ and L$_{23}$ M$_{23}$ M$_{45}$/L$_{23}$ M$_{23}$ M$_{23}$ Auger intensity ratios in transition metal oxides and sulphides are shown to be directly related to the number of valence electrons in the metal as well as to its oxidation state. The metal Auger intensity ratios provide a unique probe, independent of O (KLL) intensity, to study surface oxidation states of metals. These intensity ratios have been effectively employed to investigate surface oxidation of nickel, iron and copper. The oxidation studies have unravelled some interesting aspects of surface oxidation.

A rational approach to the synthesis of one-dimensional acoustic filters

The velocity ratio algorithm developed from a heuristic study of transfer matrix multiplication has been employed to bring out the relative effects of the elements constituting a linear, one-dimensional acoustic filter, the overall dimensions of which are fixed, and synthesize a suitable straight-through configuration for a low-pass, wide-band, non-dissipative acoustic filter. The potential of the foregoing approach in applications to the rational design of practical acoustic filters such as automotive mufflers is indicated.