Studies in crystal engineering. Photochemical and crystallographic investigations of bromocoumarins and (±)-7-(p-bromobenzylidene)piperitone

Studies in crystal engineering. Photochemical and crystallographic investigations of bromocoumarins and (±)-7-(p-bromobenzylidene)piperitone

Dental identification and aspects of medico-legal investigations of the Finnish victims of the Sumatra-Andaman earthquake on 26 December 2004

Tsunami waves of the Sumatra-Andaman earthquake on 26 December 2004 claimed approximately 230 000 lives and started the biggest identification operation in Interpol's history. The aim of this study was to resolve methods of the identification and results received. The viewpoint is mainly that of forensic odontology, but also includes other means of identification and results of the medico-legal examination performed in Finland. Of the 5395 victims in Thailand, approximately 2 400 were foreigners from 36 nations including 177 Finnish nationals. Additionally, a Finnish woman perished in Sri Lanka and a severely injured man after the evacuation in a hospital. The final numbers of missing persons and dead bodies registered in the Information Management Centre in Phuket,Thailand, were 3 574 ante-mortem (AM) and 3 681 post-mortem (PM) files. The number of identifications by December 2006 was 3 271 or 89% of the victims registered. Of Finnish victims, 172 have been identified in Thailand and 163 repatriated to Finland. One adult and four children are still missing. For AM data, a list of Finnish missing persons including 178 names was published on 30 December 2004. By February 2005 all useful dental AM data were available. Five persons on the list living in Finland lacked records. Based on the AM database, for the children under age 18 years (n=60) dental identification could be established for 12 (20%). The estimated number for adults (n=112) was 96 (86%). The final identification rate, based on PM examinations in Finland, was 14 (25%) for children (n= 56) and 98 (90%) for adults (n= 109). The number of Finnish victims identified by dental methods, 112 (68%), was high compared to all examined in Thailand (43%). DNA was applied for 26 Finnish children and for 6 adults, fingerprints for 24 and 7, respectively. In 12 cases two methods were applied. Every victim (n=165) underwent in Finland a medico-legal investigation including an autopsy with sampling specimens for DNA, the toxicological and histological investigation. Digital radiographs and computed tomography were taken of the whole body to verify autopsy findings and bring out changes caused by trauma, autolysis, and sampling for DNA in Thailand. Data for identification purposes were also noted. Submersion was the cause of death for 101 of 109 adults (92.7%), and trauma for 8 (7.3%). Injuries were 33 times contributing factors for submersion and 3 times for trauma-based death. Submersion was the cause of death for 51 (92.7%) children and trauma for 4 (7.3%). Injuries were in 3 cases contributing factors in submersion and once in trauma-based death. The success of the dental identification of Finnish victims is mainly based on careful registration of dental records, and on an education program from 1999 in forensic odontology.

Synthetic investigations on illudinine: a new synthesis of methyl 8-methoxy-2,2-dimethyl-7-oxo-1,2,3,5,6,7-hexahydro-s-indacene-4-carboxylate

A new strategy for the total synthesis of methyl 8-methoxy-2,2-dimethyl-7-oxo-1,2,3,5,6,7-hexahydro-s-indacene-4-carboxylate 4, a key intermediate in the synthesis of illudalanes, is reported. The key step in this strategy is a new method of preparation of indanones from tetralones. Thus, the furfurylidene derivative of 6-methoxy-3,4-dihydronaphthalen-1-(2H)-one is oxidised to the dicarboxylic acid 9a which is cyclodehydrated to methyl 7-methoxy-1-oxoindan-4-carboxylate 10. Similar reactions on the tetrahydronaphthalenone 25, obtained from 6-methoxy-1,2,3,4-tetrahydronaphthalene-7-carbaldehyde 11 by sequential transformations including a regiospecific benzylic oxidation resulted in the hexahydro-s-indacenone 4, thus completing a formal synthesis of illudinine 1.

1, 2-Bis (diphenylphosphino) etane bridged dinuclear copper (I) complexes: Investigations of solid state and solution structures by CP/MAS31P NMR spectroscopy, X-ray crystallography, IR spectroscopy and solution 31P NMR and 63Cu NMR spectroscopy

Three different complexes of copper (I) with bridging 1, 2-bis(diphenylphosphino)ethane (dppe), namely [Cu2 (mu-dppe) (CH3CN)6] (ClO4)2 (1), [Cu2 (mu-dppe)2 (CH3 CN)2] (ClO4)2 (2), and [Cu2 (mu-dppe) (dppe)2 (CH3CN)2] (ClO4)2 (3) have been prepared. The structure of [Cu2 (mu-dppe) (dPPe)2 (CH3CH)2] (ClO4)2 has been determined by X-ray crystallography. It crystallizes in the space group PT with a=12.984(6) angstrom, b=13.180(6) angstrom, c=14.001(3) angstrom, alpha=105.23(3), beta=105.60(2), gamma=112.53 (4), V=1944 (3) angstrom3, and Z=1. The structure was refined by least-squares method with R=0.0365; R(w)=0.0451 for 6321 reflections with F0 greater-than-or-equal-to 3 sigma (F0). The CP/MAS P-31 and IR spectra of the complexes have been analysed in the light of available crystallographic data. IR spectroscopy is particularly helpful in identifying the presence of chelating dppe. P-31 chemical shifts observed in solid state are very different from those observed in solution, and change significantly with slight changes in structure. In solution, complex 1 remains undissociated but complexes 2 and 3 undergo extensive dissociation. With a combination of room temperature H-1, Cu-63, and variable temperature P-31 NMR spectra, it is possible to understand the various processes occurring in solution.

Electronic absorption and emission spectroscopic investigations of the interaction of the fullerenes, C60 and C70, with amines and aromatic molecules

Electronic absorption spectroscopy and fluorescence spectroscopy have been used to investigate the interaction of the fullerenes C60 and C70 with diethylaniline, and with aromatic solvents such as benzene. C60 interacts weakly with aromatic amines in the ground state while C70 does not interact at all. Steady state fluorescence emission and lifetime measurements show that both C60 and C70 form excited state complexes (exciplexes) with the amines in non-aromatic solvents such as methylcyclohexane, but not in benzene. In benzene, only fluorescence quenching is observed due to the interaction between the π systems of the aromatic solvent and the fullerene in the ground state. This is also borne out by the systematic study of solvent effects on the absorption and emission spectra of the fullerenes.

Fe-57 Mössbauer and Mo K-EXAFS Investigations of MoxFe3-xO4, an Interesting Mixed-Valent Oxide System

Ferrites of the formula MoxFe3-xO4, prepared by a soft-chemistry route, show mixed valence states of both iron and molybdenum cations. Mössbauer studies show that Fe2+ and Fe3+ ions are present on both the A and B sites, giving Fe an average oxidation state between 2+ and 3+. Molybdenum is present in the 3+ and the 4+ states on the B sites. The presence of Mo in the 3+ state has been established by determining the Mo3+-O distance (2.2 Å), for the first time, by Mo K-EXAFS. The mixed valence of Fe on both the A and B sites and of Mo on the B sites is responsible for the fast electron transfer between the cations. All the Mössbauer parameters including the line width show a marked change at a composition (x ? 0.3) above which the concentration of Fe2+A increases rapidly.

Spectroscopic investigations of phase transitions in complex solids

Spectroscopic methods have provided information of seminal importance in understanding phase transitions in solids. After briefly examining some fundamental concept related to phase transitions, we shall discuss several case studies particularly involving the use of vibrational (IR and Raman) spectroscopy. Examples will include both order-disorder and displacive transitions. Under the former are included transitions in nitrates, ammonium halides, alkylammonium salts, plastic state of C60 and superionic conductors (specially CsHSO4). In addition, we shall discuss some aspects of incommensurate phase transitions, the glass transition and electronic phase transitions. Transitions of phosphonitrilic halide tetramers and alkane dicarboxylic acids are also examined

Investigations on the Corona performance of a Ceramic disc Insulators integrated with Field Reduction Electrode

This paper presents laboratory investigations on the visible corona and discharge radio noise. Experimental investigations are carried on various types of normal and anti-fog types of ceramic disc insulator at the recently established artificial pollution experimental facility. The results obtained from the experimental investigations show better performance for the disc insulators fitted with field reduction electrodes. In addition to the corona and radio noise investigations the comparisons are also made for the experimental results of the potential distribution across the insulator string (with and without filed reduction electrode) with the simulation results obtained by using Surface Charge Simulation Method.

Field investigations of the 30 September 1993 earthquake in Maharashtra

An engineering field study of the 30 September Marathwada earthquake is reported. The study covered Osmanabad, Latur, Sholapur, Bijapur, Gulbarga and Bidar districts. The level of ground acceleration was estimated based on tilting of free standing objects. The study shows that the epicentral intensity has been VIII on the UNESCO scale. The horizontal ground acceleration near the epicentre has been estimated to be about 0.2 g.

Investigations of carbon nanotubes

Experiments have been carried out to optimize the yields of carbon nanotubes obtained by the arc-evaporation of graphite. Other types of carbon particles such as nanocrystalline graphite usually present along with the nanotubes are readily removed by heating the material in oxygen around 763 K. Clean nanotubes so obtained have been characterized by X-ray diffraction. The clean tubes are thermally more stable than graphite or fullerenes. The tips of carbon nanotubes are opened by reaction with oxygen, but more interestingly, when the oxygen produced by the decomposition of a metal oxide is used to open the tube tips, the metal formed in the process enters the nanotube. Electrical resistance of pressed pellets of clean tubes is not unlike that of graphite. Tunnelling conductance measurements on isolated tubes characterized by means of scanning tunnelling microscopy however show that the conductance gap increases with decreasing tube diameter.

Investigations Of Iron Adducts Of C-60 - Novel Fec60 In The Solid-State With Fe Inside The C-60 Cage

By carrying out contact-arc vaporization of graphite in a partial atmosphere of Fe(CO)5, an iron-adduct with C60 has been obtained. The adduct has been characterized by various techniques including mass spectrometry, Fe-57 Mossbauer spectroscopy and Fe K-EXAFS. Properties of this adduct are compared with those of an adduct prepared by solution method where Fe is clearly outside the cage. Results suggest that FeC60 obtained from the gas phase reaction has the Fe atom in the cage.

Investigations of the reduction behavior of Iron-impregnated alumina gels (Fe/AlOOH) and the formation of Fe0-Al2O3 metal-ceramic composites

Fe/AlOOH gels calcined and reduced at different temperatures have been investigated by a combined use of Mossbauer spectroscopy, x-ray diffraction, and electron microscopy in order to obtain information on the nature of the iron species formed as well as the various reduction processes. Calcination at or below 1070 K mainly gives reducible Fe3+ while calcination at higher temperatures gives substitutional Fe3+ in the form of Al2-xFexO3. The Fe3+ species in the calcined samples are, by and large, present in the form of small superparamagnetic particles. Crystallization of Al2O3 from the gels is catalyzed by Fe2O3 as well as FeAl2O4. Fe (20 wt. %)/AlOOH gels calcined at or below 870 K give FeAl2O4 when reduced in hydrogen at 1070 K or lower and a ferromagnetic Fe0-Al2O3 composite (with the metallic Fe particles >100 angstrom) when reduced at 1270 K. Samples calcined at 1220 K or higher give the Fe0-Al2O3 composite when reduced in the 870-12,70 K range, but a substantial proportion of Fe3+ remains unreduced in the form of Al2-xFexO3, showing thereby the extraordinary stability of substitutional Fe3+ to reduction even at high temperatures. Besides the ferromagnetic Fe0-Al2O3 composite, high-temperature reduction of Al2-xFexO3 yields a small proportion of superparamagnetic Fe0-Al2O3 wherein small metallic particles (<100 angstrom) are embedded in the ceramic matrix. In order to preferentially obtain the Fe0-Al2O3 composite on reduction, Fe/AlOOH gels should be calcined at low temperatures (less-than-or-equal-to 1100 K); high-temperature calcination results in Al2-xFexO3. Several modes of formation of FeAl2O4 are found possible during reduction of the gels, but a novel one is that involving the reaction, 2Fe3+ + Fe0 --> 3Fe2+.

EXAFS investigations of Ni/gamma-Al2O3 and Ni/AlPO4 catalysts and their precursors

In-situ EXAFS investigations have been carried out on Ni/gamma-Al2O3 catalysts with different metal loadings and prepared from different precursors. When the calcined precursors are reduced in hydrogen, the proportion of nickel metal formed varies with the nature of the precursor employed; NiAl2O4 is the unreduced product. The metal loading does not have any significant effect on the proportion of metal formed except in the case of the catalyst prepared by wet-impregnation, where appreciable metal is obtained only when the loading is greater than 10wt%. Ni/AlPO4 catalysts do not show the formation of NiAl2O4 and reduction to metal is complate, unlike with the Ni/gamma-Al2O3 catalysts which show only partial reduction to metal.

Review of hypersonic research investigations in IISc shock tunnel (HST1)

Real gas effects dominate the hypersonic flow fields encountered by modem day hypersonic space vehicles. Measurement of aerodynamic data for the design applications of such aerospace vehicles calls for special kinds of wind tunnels capable of faithfully simulating real gas effects. A shock tunnel is an established facility commonly used along with special instrumentation for acquiring the data for this purpose within a short time period. The hypersonic shock tunnel (HST1), established at the Indian Institute of Science (IISc) in the early 1970s, has been extensively used to measure the aerodynamic data of various bodies of interest at hypersonic Mach numbers in the range 4 to 13. Details of some important measurements made during the period 1975-1995 along with the performance capabilities of the HST1 are presented in this review. In view of the re-emergence of interest in hypersonics across the globe in recent times, the present review highlights the Suitability of the hypersonic shock tunnel at the IISc for future space application studies in India.

Structural Hypotheses And Raman-Spectroscopy Investigations Of Glasses Belonging To The B2s3-Li2s-Lii System

A previous B-11 nuclear magnetic resonance investigation of glasses belonging to the B2S3-Li2S-LiI system had allowed the authors to determine the variation of the number of three and four coordinated boron atoms with composition. These results, in addition to the observation that vitreous B2S3 quite easily forms fibres during casting, have led us to propose structural hypotheses for B2S3 based glasses, which are supported by the present Raman spectroscopy study. For vitreous B2S3 the spectra were accounted for on the basis of the various types of BS3/2 triangles proposed by the model. Molecular orbital considerations allowed us to assign the most significant lines for the binary glasses by assuming that BS3/2 triangles (with or without nonbridging sulphur atoms) and BS4 tetrahedra were present. In the ternary system, lithium iodide has been found to interact slightly on the structural entities, altering their vibrational characteristics without fundamentally modifying their nature.