Studies in the mass spectra of perfluoroaromatic derivatives of phosphorus and some selected transition metals

The mass spectra and fragmentation of a variety of fluoroaromatic compounds of Group V and some selected transition elements are discussed in some detail, aided by data from metastable defocussed experiments. Results of ,studies on the coupling reaction using unstable organotitanium chloride intermediate species are reported. The preparation of some 5-substituted octafluorodibenzophospho1es is also discussed. Rearrangements under electron bombardment resulting in the loss of heteroatom-fluoride fragments are discussed in the light of presently accepted mechanisms for these processes as are rearrangements observed in compounds involving thionophosphoryl bonds ( p=s ).

Effects of large anphiphilic ligands upon the spectra and kinetics of cytochrome C oxidase

Cytoch ro me c oxidase (ferrocytochrome c : 02 oxidoreductase ; EC 1.9. 3.1) is the terminal enzyme in the mitochondrial electron transport chain, catalyzing the transfer of electrons from ferrocytochrome c to molecular oxygen. The effects of two large amphiphilic molecules - valinomycin and dibucaine upon the spectra of the isolated enzyme and upon the activity of both isolated enzyme and enzyme in membrane systems are investigated by using spectrophotometric and oxygen electrode techniques. The results show that both valinomycin and dibucaine change the Soret region of the speetrum and cause a partial inhibition in a concentration range higher than that in which they act as ionophores. It is concluded that both valinomycin and dibucaine binding induce a conformational change of the protein structure which modifies the spectrum of the a3 CUB centre and diminishes the rate of electron transfer between cytochrome a and the binuclear centre.

Developing a numerical inverse-theory-based extraction of orientation-dependent relaxation rates from partially- relaxed spectra

Second-rank tensor interactions, such as quadrupolar interactions between the spin- 1 deuterium nuclei and the electric field gradients created by chemical bonds, are affected by rapid random molecular motions that modulate the orientation of the molecule with respect to the external magnetic field. In biological and model membrane systems, where a distribution of dynamically averaged anisotropies (quadrupolar splittings, chemical shift anisotropies, etc.) is present and where, in addition, various parts of the sample may undergo a partial magnetic alignment, the numerical analysis of the resulting Nuclear Magnetic Resonance (NMR) spectra is a mathematically ill-posed problem. However, numerical methods (de-Pakeing, Tikhonov regularization) exist that allow for a simultaneous determination of both the anisotropy and orientational distributions. An additional complication arises when relaxation is taken into account. This work presents a method of obtaining the orientation dependence of the relaxation rates that can be used for the analysis of the molecular motions on a broad range of time scales. An arbitrary set of exponential decay rates is described by a three-term truncated Legendre polynomial expansion in the orientation dependence, as appropriate for a second-rank tensor interaction, and a linear approximation to the individual decay rates is made. Thus a severe numerical instability caused by the presence of noise in the experimental data is avoided. At the same time, enough flexibility in the inversion algorithm is retained to achieve a meaningful mapping from raw experimental data to a set of intermediate, model-free

Identidty, displacement and embodiment in women's independent cinema

Ma thèse examine les déplacements multiples – déportation, exil, voyage – et l‟expérience diasporique de différentes communautés ethniques dans le cinéma indépendant de trois réalisatrices et artistes contemporaines : Julie Dash, Rea Tajiri et Trinh T. Minh-ha. J‟analyse la déconstruction et reconstruction de l‟identité à travers le voyage et autres déplacements physiques ainsi que les moyens d‟expression et stratégies cinématographiques utilisées par ces artistes pour articuler des configurations identitaires mouvantes. Je propose de nouvelles lectures de la position des femmes dans des milieux culturels différents en considérant la danse comme une métaphore de la reconfiguration de l‟identité féminine qui se différencie et s‟émancipe des traditions culturelles classiques. Les expériences de l‟histoire et de la mémoire, qui sont vécues dans les corps des femmes, sont aussi exprimées par le biais des relations intermédiales entre la photographie, la vidéo et le film qui proposent des images de femmes variées et complexes.

Structure Absorption Spectra Correlation in a Series of 2,6-Dimethyl-4-arylpyrylium Salts

A combined experimental and theoretical study of the absorption spectra of a group of closely related pyrylium perchlorates 1-11 are presented. Minor changes in the position of the substituents lead to drastic changes in the absorption spectra in this series of compounds. We have attempted to explain the observed changes using the x,y-band notation developed by Balaban and co-workers. Absorption spectra of all compounds are compared with results from time-dependent density functional theory (TDDFT) and Zerner’s intermediate neglect of differential overlap (ZINDO/S) level calculations. Results of the calculations are in good agreement with experimental observations and an interesting correlation between Balaban’s notations and the MO transitions are obtained for simple derivatives. It is suggested that for more complex systems such as R- and â-naphthyl substituted systems, the empirical method is not appropriate.

Raman spectra of polymethyl methacrylate optical fibres excited by a 532 nm diode pumped solid state laser

Polymethyl methacrylate (PMMA) optical fibres are fabricated by a preform drawing process. The Raman spectra of PMMA fibres are recorded using a diode pumped solid state laser emitting at 532 nm and a CCD-spectrograph in the 400–3800 cm−1 range. The variation of the Raman intensity with the length of the optical fibre is studied. Investigations are carried out on the variation of FWHM of the Raman peak at 2957 cm−1 with the length of the optical fibre and pump power. The differential scattering cross section and gain coefficient of the Raman peak at 2957 cm−1 in PMMA are calculated in relation to that of toluene.

Raman spectra of polymethyl methacrylate optical fibres excited by a 532 nm diode pumped solid state laser

Polymethyl methacrylate (PMMA) optical fibres are fabricated by a preform drawing process. The Raman spectra of PMMA fibres are recorded using a diode pumped solid state laser emitting at 532 nm and a CCD-spectrograph in the 400–3800 cm−1 range. The variation of the Raman intensity with the length of the optical fibre is studied. Investigations are carried out on the variation of FWHM of the Raman peak at 2957 cm−1 with the length of the optical fibre and pump power. The differential scattering cross section and gain coefficient of the Raman peak at 2957 cm−1 in PMMA are calculated in relation to that of toluene

NIR to UV absorption spectra and the optical constants of phthalocyanines in glassy medium

Optical absorption studies of phthalocyanines (Pc-s) in borate glass matrix have been reported for the first time. Measurements have been done corresponding to photon energies between 1.1 and 6.2 eV for free base, manganese, iron, nickel, molybdenum, cobalt and copper phthalocyanines. Several new discrete transitions are observed in the UV–vis region of the spectra in addition to a strong continuum component of absorption in the IR region. Values of some of the important optical constants viz. absorption coefficient (α), molar extinction coefficient (ε), absorption cross-section (σa), band width (Δλ), electric dipole strength (q2) and oscillator strength (f) for the relevant electronic transitions are also presented. All the data reported for Pc-s in the new matrix have been compared with those corresponding to solution, vapor and thin film media.

Overtone Spectra of 1,2-Dichloro-And Dibromo-Ethanes in the Near Infrared Region

The vibrational overtone spectra 0f the liquid phase 1,2-dichloroethane and 1,2-dibromoethane in the spectral regions of CH stretching local mode overtones corresponding to delta v CH= = 2 to delta v CH=5 are reported. The observed spectral features are assigned using the local mode model. LocaI mode frequencies WCH and diagonal local mode anharmonicities XCH are obtained from an analysis of the spectra. The local-local combinations observed are interpreted on the basis of a coupled CH oscillator model hamiltonian. Local-normal combinations show complex structures and their possible assignments are given.

Overtone spectra of styrene and polystyrene in the visible and near infrared regions

Vibrational overtone spectra of styrene (liquid) and polystyrene (solid), studied by the laser-induced thermal lens (for ΔV=6) and the conventional near infrared absorption (for ΔV=3–5) techniques, are reported. For polystyrene, the overtone energy-bond length correlation predicts that the aryl CH bonds are ∼0.0005 Å longer than that in benzene, while no such conclusions could be drawn on styrene. Thesp 3 CH overtones in polystyrene are observed on the low energy side of the aryl CH overtones.

Hysteresis in a system driven by either generalized force or displacement variables: martensitic phase transition in single-crystalline Cu-Zn-Al

We report on experiments aimed at comparing the hysteretic response of a Cu-Zn-Al single crystal undergoing a martensitic transition under strain-driven and stress-driven conditions. Strain-driven experiments were performed using a conventional tensile machine while a special device was designed to perform stress-driven experiments. Significant differences in the hysteresis loops were found. The strain-driven curves show reentrant behavior yield point which is not observed in the stress-driven case. The dissipated energy in the stress-driven curves is larger than in the strain-driven ones. Results from recently proposed models qualitatively agree with experiments.

Measurement and simulation of anisotropy in the Infrared and Raman spectra of beta-FeSi2 single crystals

In this paper we show that the orthorhombic phase of FeSi2 (stable at room temperature) displays a sizable anisotropy in the infrared spectra, with minor effects in the Raman data too. This fact is not trivial at all, since the crystal structure corresponds to a moderate distortion of the fluorite symmetry. Our analysis is carried out on small single crystals grown by flux transport, through polarization-resolved far-infrared reflectivity and Raman measurements. Their interpretation has been obtained by means of the simulated spectra with tight-binding molecular dynamics.