Synthesis and spectral studies of methyl heterocylic systems

2-Carboxy-2?-methyldiphenyl sulfide was prepared by the Ullmann reaction and cyclodehydrated by sulfuric acid to afford 4-methylthioxanthone. 1-Methylthioxanthone was separated from the reaction mixture obtained upon cyclodehydration of 2-carboxy-3f-methyldiphenyl sulfide. In addition, 1-, 2-, 3- and 4-methylthioxanthone 10,10-dioxides were synthesized by oxidation of the corresponding thioxanthones. o-, m- and p-N-Tolylanthranilic acids were prepared by the Ullmann reaction and used as precursors for the preparation of 1-, 2- and 4- methyl-9-chloroacridine and finally 1-, 2-, 3- and 4-methylacridone. High resolution, 60 MHz PMR spectra were obtained on the four monomethyl isomers of xanthone, thioxanthone, thioxanthone 10,10-dioxide and acridone, and on 1-, 2- and 4-methyl-9-chloroacridine. For some compounds, coupling of all three different aromatic protons to the methyl was observed, two of the couplings typically being smaller than the third. With the large (ortho) coupling being on the order of 0.5 to 1.0 Hz, it was necessary to decouple the aromatic part of the spectrum. The magnitude of the ortho benzylic constant may be related to an incomplete Tr-bond delocalization in the molecules.

The Effectiveness of the precision fluency shaping program controlling stuttering behaviour in adults

This study was done to test the effectiveness of the Precision Fluency Shaping Program in controlling stuttering behaviour in adults. Two sites were chosen, each using the Precision Fluency Shaping Program to treat stuttering. At each clinic, a Speech Patbologist made a random selection of the subjects' pre- and post-therapy video-taped interviews, totalling 20 in all. During the interviews, the clients were asked questions and re~d a short passage to determine the frequency of stuttering in natural conversation and in reading. Perceptions of Stuttering Inventory questionnaires vvere also filled in before and after therapy. Two judges were trained to identify stuttering behaviour, and were given an inter-rater reliability test at selected intervals throughout the study. Protocols",:m.a;d;6 of each interview tape, were scored for (a) stuttering behaviour and (b) words spoken or read. An Analysis of Variance Repeated Measures Test was used to compare before and after scores of conversations, readings, and Perceptions of Stuttering Inventory to determine whether the Precision Fluency Shaping Program controlled stuttering behaviour significantly. A Pearson R Correlation Test was also administered to determine if a relationship existed bet\veen Perceptions of Stuttering Inventory and (i) conversation and (ii) reading scores.

Spectral Reflectance Characteristics of Kimberlite Indicator Minerals and Other Selected Mineral Grains

High chromium content in kimberlite indicator minerals such as pyrope garnet and diopside is often correlated with the presence of diamonds. In this study, kimberlite indicator minerals were examined using visible light reflectance spectroscopy to determine if chromium content can be correlated with spectral absorption features. The depth of absorption features in the visible spectral region were correlated with the molecular percentage of chromium and other first series transition metal elements obtained by electron microprobe data. In the visible part of the spectrum, chromium is evident by 3 absorption features in the pyrope reflectance spectrum; one isolated and narrow feature at the wavelength 689 nm was used to correlate with the chromium mol %. The isolation of this feature in the pyrope spectra is advantageous since it is not directly affected by other proximal absorption bands that could be caused by other transition metals. Analysis of the feature indicates that as grain volume increases the depth of the absorption feature will also increase. Clustering grain volumes into fractions yields better correlation between absorption depth and mol % chromium. Other types of garnet (almandine, grossular, spessartine) and kimberlite indicator minerals (olivine, diopside, chromite, ilmenite) were analyzed to determine if other absorption features could be used to predict the proportion of specific transition metal elements. Diopside in particular illustrates the same isolated chromium absorption feature as pyrope and may indicate mol percent but needs further study with larger sample sets.

The Influence of the Media on Shaping Perceptions of Leadership in Sport: A Within and Between Groups Design

An experimental design that included both between-group and within-group designs was used to assess media influence on perceptions of sport leadership. Participants were recruited and randomly assigned to three groups, where each group completed two separate survey sessions regarding leader personality traits and behaviours. During the second survey session, experimental Groups 1 and 2 watched a video on a separate, respective sport leader prior to filling out the survey. There were a total of 104 participants (N = 104) for the first session, and 99 (N = 99) participants completed the second session. One-way ANOVA, factorial repeated measures ANOVA, and ANCOVA were used for data analysis. Results indicate a significant change in Group 2’s results after watching the video clip, thus rejecting the null hypotheses. Results and implications are discussed, highlighting their relationships to sport and media related theories and sport management practice.

An Autoregressive Spectral Density Estimator at Frequency Zero for Nonstationarity Tests.

Many unit root and cointegration tests require an estimate of the spectral density function at frequency zero at some process. Kernel estimators based on weighted sums of autocovariances constructed using estimated residuals from an AR(1) regression are commonly used. However, it is known that with substantially correlated errors, the OLS estimate of the AR(1) parameter is severely biased. in this paper, we first show that this least squares bias induces a significant increase in the bias and mean-squared error of kernel-based estimators.

The role of ‘Shared Memories’ in shaping nationalist movements : a comparative historical analysis of the Flemish and Québécois nationalist movements

Les mouvements nationalistes flamands et québécois divergent en concernant leur structure; par exemple le nationalisme flamand s'est développé comme un mouvement chrétien-démocrate, alors que le nationalisme québécois contemporain s’est galvanisé autour d'une idéologie laïque de gauche. Par ailleurs, il existe un contraste entre les poids sociodémographique, politique et économique portés par la région de Flandres en Belgique, et ceux portés dans la province du Québec au Canada. Cependant, malgré les influences divergentes structurelles et systémiques, les mouvements nationalistes flamand et québécois ont développé et maintenu des profils très similaires. Par exemple, les deux mouvements nationalistes se définissent par une distinction ethnolinguistique, les deux ont un discours nationaliste parallèle axé sur la nécessité de préserver et de protéger la langue et la culture de la communauté nationale, et les deux se concentrent sur l'obtention d'une redistribution des pouvoirs culturels et politiques. Dans ce mémoire, nous proposons que le profil nationaliste ressemblant du mouvement nationaliste flamand et québécois puisse être expliqué par le développement d'un « nationalisme ethnolinguistique de contestation », qui était initialement mis en place par les nationalistes flamands et québécois cherchant à corriger les effets d'une « division culturelle du travail ». Ce sentiment d’un nationalisme de contestation ethnolinguistique est instrumentalisé et perpétué par les nationalistes flamands et québécois en évoquant certains « souvenirs partagés », qui sont trouvés dans le récit historique de la communauté nationale. Ces souvenirs partagés, ainsi que leurs représentations symboliques, reflètent les sentiments de protestation, injustice et victimisation, qui sont vitaux pour les nationalistes flamands et québécois dans le maintien de leur expression parallèlement à un nationalisme de contestation ethnolinguistique en Flandres et au Québec.

Le personnage-figurant : absence de monde et corps spectral dans l’œuvre de Béla Tarr

Ce mémoire examine le rapport du visible à l’invisible dans l’œuvre du cinéaste hongrois Béla Tarr afin de montrer comment cette œuvre fait sa plus grande place, quoique le plus souvent sous la forme d’une absence-présence, à la question du néant et de la mort. À travers une étude tripartite, tour à tour concernant le traitement cinématographique et thématique du monde, du temps et du personnage et de leurs fonctions, l’objectif de cette recherche est celui de montrer comment cette œuvre soustractive interroge le rapport de l’existant à un monde qui fait défaut. C’est la promesse, en partie telle que théorisée par Peter Sloterdijk, qui permettra ultimement d’éclairer la démarche tragique des personnages tarriens : lutte contre la mort au moyen d’un constant effort de soi et ce, jusqu’à l’épuisement radical. La notion de personnage-figurant développée dans ce mémoire se propose d’articuler ensemble les valeurs figuratives et thématiques communes aux différents personnages qui traversent l’œuvre afin d’en mieux comprendre, malgré les ruptures stylistiques et narratives, la continuité. Enfin, le dialogue engagé ici entre l’œuvre du cinéaste et certains concepts-clé de la tradition philosophique (le monde, le soi, le temps) entend montrer comment la première ouvre des pistes pertinentes pour une réflexion sur le sujet contemporain et son époque.

Structural, Spectral, Biological and Electrochemical Studies Of Some 3d Transition Metal Complexes of O-N-S and N-N-S Donor Ligands

The primary aim of these investigations was to probe the spectroscopic, electrochemical, biological and single crystal X-ray diffraction studies of some selected transition metal complexes of 4N-monosubstituted thiosemicarbazones. Transition metal complexes with thiosemicarbazones exhibit a wide range of stereochemistries and possess potential biological activity. Metal complexes of thiosemicarbazones are proved to have improved pharmacological and therapeutic effects. The studies are conducted to bring about a fair understanding of the structure activity relationship and to develop certain effective and economical metal-based antimicrobial agents. Study showed that the thiosemicarbazones have antibacterial, antiviral and antiproliferative properties and hence used against tuberculosis, leprosy, psoriasis, rheumatism, trypanosomiasis and coccidiosis. Certain thiosemicarbazones showed a selective inhibition of HSV and HIV infections. The insolubility of most thiosemicarbazones in water causes difficulty in the oral administration in clinical practice. Transition metal complexes are found to have more activity than uncombined thiosemicarbazones. They exhibit a variety of denticity and can be varied by proper substitution. The stereochemistry assumed by the thiosemicarbazones during the coordination with transition metal ions depends on the factors such as preparative conditions and availability of additional bonding site in the ligand moiety and charge of the ligand. The resulting complexes exhibited a wide range of stereochemistries and have biomimic activity and potential application as sensors.

Synthesis, Spectral Characterization, Structural Studies and Biological Investigations of Transition Metal Complexes of Some Acid Hydrazones

This study concentrates the chemical properties of hydrazones due to its chelating capability and their pharmacological applications. Studies cover the preparation of different acid hydrazones and their structural studies and studies on their antimicrobial activity, synthesis and spectral characterization of different complexes of copper oxovanadium, manganese, nickel etc. Effect of incorporation of heterocyclic bases to the coordination sphere, change in the biological activity of acid hydrazones upon coordination, development of X-ray quality single crystals and its X-ray diffraction studies, studies on the redox behavior of the coordinated metal ions and correlation between the stereochemistry and biological activities.

Spectral Characteristics of the Blood of Streptozotocin Diabetic Rats using Photoacoustic Technique

Optical absorption characteristics of rat blood affected by diabetes has been studied using photoacoustic (PA) technique. PA spectrum of blood depends on the molecular structure of haemoglobin. The peak value ratio ylQ increases with increase in the diabetic state. Externally added glucose to normal blood does not show any increase in y//3 ratio as seen in the diabetic condition . The increase in yl,8 ratio may be due to the decrease in DPG level and the resultant shift from R -> T conformation of majority of diabetic haemoglobin.

Structural and Spectral Investigations of Transition Metal Complexes Of Di-2-Pyridyl Ketone N (4), N (4)-Disubstituted Thiosemicarbazones

The study deals with structural and spectral investigations of transition metal complexes of di-2-pyridyl ketone N(4),N(4)-disubstituted thiosemicarbazones. The main objective and scope of the work deals with di-2-pyridyl ketone N(4),N(4)-disubstituted thiosemicarbazones are quardridentate NNNS donor ligands. To chosen this ligand for study because, the ligands are prepared and characterized for the first time, since there are two pyridyl nitorgens, dimmers and polymers of complexes may result leading to interesting structural aspects. The work includes the preparation of the thiosemicarbzones and their structural and spectral studies, synthesis and spectral characterization of complexes of copper(II),,nickel(II),manganese(II), dioxovanadium(V),cobalt(III),zinc(II),cadmium(II) of the ligand HL, synthesis and spectral characterization of complexes of copper(II),manganese(II), of the ligand HL and the development of X-ray quality crystals and its X-ray diffraction studies. The structural characterization techniques are elemental analysis, conductivity measurements, magnetic measurements, electronic spectroscopy, H NMR spectroscopy, Infrared spectroscopy and X-ray crystallography.

Structural, Spectral, Biological and Electrochemical Studies Of Some 3d Transition Metal Complexes of O-N-S and N-N-S Donor Ligands

The primary aim of these investigations was to probe the spectroscopic, electrochemical, biological and single crystal X-ray diffraction studies of some selected transition metal complexes of 4N-monosubstituted thiosemicarbazones. Transition metal complexes with thiosemicarbazones exhibit a wide range of stereochemistries and possess potential biological activity. Metal complexes of thiosemicarbazones are proved to have improved pharmacological and therapeutic effects. The studies are conducted to bring about a fair understanding of the structure activity relationship and to develop certain effective and economical metal-based antimicrobial agents. Study showed that the thiosemicarbazones have antibacterial, antiviral and antiproliferative properties and hence used against tuberculosis, leprosy, psoriasis, rheumatism, trypanosomiasis and coccidiosis. Certain thiosemicarbazones showed a selective inhibition of HSV and HIV infections. The insolubility of most thiosemicarbazones in water causes difficulty in the oral administration in clinical practice. Transition metal complexes are found to have more activity than uncombined thiosemicarbazones. They exhibit a variety of denticity and can be varied by proper substitution. The stereochemistry assumed by the thiosemicarbazones during the coordination with transition metal ions depends on the factors such as preparative conditions and availability of additional bonding site in the ligand moiety and charge of the ligand. The resulting complexes exhibited a wide range of stereochemistries and have biomimic activity and potential application as sensors