Sonically induced narrowing of the NMR spectra of solids and other novel NMR techniques

A typical liquid state NMR spectrum is composed of a number of discrete absorptions which can be readily interpreted to yield detailed information about the chemical environment of the nuclei found within the sample. The same cannot be said about the spectra of solid samples. For these the absorptions are typically broad, featureless and yield little information directly. This situation may be further exacerbated by the characteristically long T1 values of nuclei bound within a solid lattice which, consequently, require long inter-sequence delays that necessitate lengthy experiments. This work attempts to address both of these inherent problems. Classically, the resolution of the broad-line spectra of solids into discrete resonances has been achieved by imparting to the sample coherent rotation about specific axes in relation to the polarising magnetic field, as implemented in the magic-angle spinning (MAS) [1], dynamic angle spinning (DAS) [2] and double rotation (DOR) [3] NMR experiments. Recently, an alternative method, sonically induced narrowing of the NMR spectra of solids (SINNMR) [4], has been reported which yields the same well resolved solid-state spectra as the classic solid-state NMR experiments, but which achieves the resolution of the broad-line spectra through the promotion of incoherent motion in a suspension of solid particles. The first part of this work examines SINNMR and, in particular, concentrates on ultrasonically induced evaluation, a phenomenon which is thought to be essential to the incoherent averaging mechanism. The second part of this work extends the principle of incoherent motion, implicit in SINNMR, to a new genre of particulate systems, air fluidized beds, and examines the feasibility of such systems to provide well resolved solid state NMR spectra. Samples of trisodium phosphate dodecahydrate and of aluminium granules are examined using the new method with partially resolved spectra being reported in the case of the latter.

Matrix-assisted diffusion-ordered spectroscopy:application of surfactant solutions to the resolution of isomer spectra

The component spectra of a mixture of isomers with nearly identical diffusion coefficients cannot normally be distinguished in a standard diffusion-ordered spectroscopy (DOSY) experiment but can often be easily resolved using matrix-assisted DOSY, in which diffusion behaviour is manipulated by the addition of a co-solute such as a surfactant. Relatively little is currently known about the conditions required for such a separation, for example, how the choice between normal and reverse micelles affects separation or how the isomer structures themselves affect the resolution. The aim of this study was to explore the application of sodium dodecyl sulfate (SDS) normal micelles in aqueous solution and sodium 1,4-bis(2-ethylhexyl)sulfosuccinate (AOT) aggregates in chloroform, at a range of concentrations, to the diffusion resolution of some simple model sets of isomers such as monomethoxyphenols and short chain alcohols. It is shown that SDS micelles offer better resolution where these isomers differ in the position of a hydroxyl group, whereas AOT aggregates are more effective for isomers differing in the position of a methyl group. For both the normal SDS micelles and the less well-defined AOT aggregates, differences in the resolution of the isomers can in part be rationalised in terms of differing degrees of hydrophobicity, amphiphilicity and steric effects. Copyright © 2012 John Wiley & Sons, Ltd.

Turbulent broadening of optical spectra in ultralong Raman fiber lasers

We study the properties of radiation generated in ultralong fiber lasers and find an interesting link between these optical systems and the theory of weak wave turbulence. Experimental observations strongly suggest that turbulentlike weak interactions between the multitude of laser cavity modes are responsible for practical characteristics of ultralong fiber lasers such as spectra of the output radiation.

The vibrational spectra of rectangular plates

The wire drive pulse-echo system has been extensively used to excite and measure modes of vibration of thin rectangular plates. The frequency spectra of different modes have been investigated as a function of the material elastic moduli and the plate geometry. Most of the work was carried out on isotropic materials. For square plates a wide selection of materials were used. These were made isotropic in their in-plane dimensions where the displacements are taking place. The range of rnaterials enabled the dependence on Poisson's ratio to be investigated. A method of determining the value of Poisson's ratio resulted from this investigation. Certain modes are controlled principally by the shear modulus. Of these the fundamental has two nodal lines across the plate surface. One of them, which has nodes at the corners, (the Lame mode) is uniquely a pure shear mode where the diagonal is a full wave length. One controlled by the Young's modulus has been found. The precise harmonic relationship of the Lame mode series in square and rectangular plates was established. Use of the Rayleigh-Lamb equation has extended the theoretical support. The low order modes were followed over a wide range of sides ratios. Two fundamental types of modes have been recognised; These are the longitudinal modes where the frequency is controlled by the length of the plate only and the 2~f product has an asymptotic value approaching the rod velocity. The other type is the in-plane flexural modes (in effect a flexurally vibrating bar where the -2/w is the geometrical parameter). Where possible the experimental work was related to theory. Other modes controlled by the width dimension of the plate were followed. Anisotropic materials having rolled sheet elastic symmetry were investigated in terms of the appropriate theory. The work has been extended to examine materials from welds in steel plates.

Design and development of a time of flight fast scattering spectrometer : a quantitative surface analysis technique and a new approach towards the experimental investigation of the surface particle interactions

A new surface analysis technique has been developed which has a number of benefits compared to conventional Low Energy Ion Scattering Spectrometry (LEISS). A major potential advantage arising from the absence of charge exchange complications is the possibility of quantification. The instrumentation that has been developed also offers the possibility of unique studies concerning the interaction between low energy ions and atoms and solid surfaces. From these studies it may also be possible, in principle, to generate sensitivity factors to quantify LEISS data. The instrumentation, which is referred to as a Time-of-Flight Fast Atom Scattering Spectrometer has been developed to investigate these conjecture in practice. The development, involved a number of modifications to an existing instrument, and allowed samples to be bombarded with a monoenergetic pulsed beam of either atoms or ions, and provided the capability to analyse the spectra of scattered atoms and ions separately. Further to this a system was designed and constructed to allow incident, exit and azimuthal angles of the particle beam to be varied independently. The key development was that of a pulsed, and mass filtered atom source; which was developed by a cyclic process of design, modelling and experimentation. Although it was possible to demonstrate the unique capabilities of the instrument, problems relating to surface contamination prevented the measurement of the neutralisation probabilities. However, these problems appear to be technical rather than scientific in nature, and could be readily resolved given the appropriate resources. Experimental spectra obtained from a number of samples demonstrate some fundamental differences between the scattered ion and neutral spectra. For practical non-ordered surfaces the ToF spectra are more complex than their LEISS counterparts. This is particularly true for helium scattering where it appears, in the absence of detailed computer simulation, that quantitative analysis is limited to ordered surfaces. Despite this limitation the ToFFASS instrument opens the way for quantitative analysis of the 'true' surface region to a wider range of surface materials.

Evaluation of the sonically induced narrowing of nuclear magnetic resonance spectra of solids

The Nuclear Magnetic Resonance (NMR) spectra of liquids contain a wealth of quantitative information that may be derived, for instance, from chemical shifts and spin-spin couplings. The available information depends on the incoherent rapid molecular motion that causes complicating effects present in the solid state to average to zero. Whereas liquid state NMR spectra show narrow lines, the corresponding NMR spectra from the solid state are normally composed of exceedingly broad resonance lines due to highly restricted molecular motion. It is, therefore, difficult to obtain directly as detailed information from the spectra of solids as from those derived from the liquid state. Studies on a new technique (SINNMR, the sonically induced narrowing of the NMR spectra of solids) to remove line broadening effects in the NMR spectra of the solid state are reported within this thesis. SINNMR involves narrowing the NMR absorptions from solid particles by irradiating them with ultrasound when they are suspended in a support liquid. It is proposed that ultrasound induces incoherent motion of the suspended particles, producing motional characteristics of the particles similar to those of rather large molecules. The first report of apparently successful experiments involving SINNMR[1] emphasised both the irreproducibility of the technique and the uncertainty regarding its true origin. If SINNMR can be made reproducible and the effect definitively attributed to the sonically induced incoherent motional averaging of particles, the technique could offer a simple alternative to the now classical magic-angle spinning (MAS) NMR[2] and the recently reported dynamic angle spinning (DAS)[3] and double rotation (DOR)[4] techniques. Evidence is presented in this thesis to support the proposal that ultrasound may be used to narrow the NMR spectral resonances from solids by inducing incoherent motion of particles suspended in support liquids and, additionally, for some solids, by inducing rotational motion of molecular constituents in the lattices of solids. Successful SINNMR line narrowing using 20 kHz ultrasound is reported for a variety of samples: including trisodium orthophosphate, polytetrafluoroethylene and aluminium alloys. Investigations of SINNMR line narrowing in trisodium phosphate have revealed the relationship between ultrasonic power, particle size and support liquid density for the production of optimum SINNMR conditions. It is also proposed that the incoherent motion of particles induced by 20 kHz ultrasound can originate from interactions between acoustically induced cavitation microjets and particles.

Dielectric and electro-optical properties of some cyanobiphenyl liquid-crystals

A variety of methods have been reviewed for obtaining parallel or perpendicular alignment in liquid-crystal cells. Some of these methods have been selected and developed and were used in polarised spectroscopy, dielectric and electro-optic studies. Also, novel dielectric and electro-optic cells were constructed for use over a range of temperature. Dielectric response of thin layers of E7 and E8 (eutectic mixture liquid-crystals) have been measured in the frequency range (12 Hz-100 kHz) and over a range of temperature (183-337K). Dielectric spectra were also obtained for supercooled E7 and E8 in the Hz and kHz range. When the measuring electric field was parallel to the nematic director, one loss peak (low-frequency relaxation process) was observed for E7 and for E8, that exhibits a Debye-type behaviour in the supercooled systems. When the measuring electric field was perpendicular to the nematic director, two resolved dielectric processes have been observed. The phase transitions, effective molecular polarisabilities, anisotropy of polarisabilities and order parameters of three liquid crystal homologs (5CB, 6CB, and 7CB), 60CB and three eutectic nematic mixtures E7, E8, and E607 were calculated using optical and density data measured at several temperatures. The order parameters calculated using the different methods of Vuks, Neugebauer, Saupe-Maier, and Palffy-Muhoray are nearly the same for the liquid crystals considered in the present study. Also, the interrelationship between density and refractive index and the molecular structure of these liquid crystals were established. Accurate dielectric and dipole results of a range of liquid-crystal forming molecules at several temperatures have reported. The role of the cyano-end group, biphenyl core, and flexible tail in molecular association, were investigated using the dielectric method for some molecules which have a structural relationship to the nematogens. Analysis of the dielectric data for solution of the liquid-crystals indicated a high molecular association, comparable to that observed in the nematic or isotropic phases. Electro-optic Kerr effect were investigated for some alkyl cyanobiphenyls, their nematic mixtures and the eutectic mixture liquid-crystals E7 and E8 in the isotropic phase and solution. The Kerr constant of these liquid crystals found to be very high at the nematic-isotropic transition temperatures as the molecules are expected to be highly ordered close to phase transition temperatures. Dynamic Kerr effect behaviour and transient molecular reorientation were also observed in thin layers of some alkyl cyanobiphenyls. Dichroic ratio R and order parameters of solutions containing some azo and anthraquinone dyes in the nematic solvent (E7 and E8), were investigated by the measurement of the intensity of the absorption bands in the visible region of parallel aligned samples. The effective factors on the dichroic ratio of the dyes dissolved in the nematic solvents were determined and discussed.

Characterizing femtosecond laser inscribed Bragg grating spectra

We present numerical modeling based on a combination of the Bidirectional Beam Propagation Method and Finite Element Method that completely describes the wavelength spectra of point by point femtosecond laser inscribed fiber Bragg gratings, showing excellent agreement with experiment. We have investigated the dependence of different spectral parameters such as insertion loss, all dominant cladding and ghost modes and their shape relative to the position of the fiber Bragg grating in the core of the fiber. Our model is validated by comparing model predictions with experimental data and allows for predictive modeling of the gratings. We expand our analysis to more complicated structures, where we introduce symmetry breaking; this highlights the importance of centered gratings and how maintaining symmetry contributes to the overall spectral quality of the inscribed Bragg gratings. Finally, the numerical modeling is applied to superstructure gratings and a comparison with experimental results reveals a capability for dealing with complex grating structures that can be designed with particular wavelength characteristics. (C) 2010 Optical Society of America

Gamma rays associated with neutron scattering in fusion reactor materials

The gamma-rays produced by the inelastic scattering of 14 MeV neutrons. in fusion reactor materials have been studied using a gamma-ray spectrometer employing a sodium iodide scintillation detector. The source neutrons are produced by the T(d,n)4He reaction using the SAMES accelerator at the University of Aston in Birmingham. In order to eliminate the large gamma-ray background and neutron signal due to the sensitivity of the sodium iodide detector to neutrons, the gamma-ray detector is heavily shielded and is used together with a particle time of flight discrimination system based on the associated particle time of flight method. The instant of production of a source neutron is determined by detecting the associated alpha-particle enabling discrimination between the neutrons and gamma-rays by their different time of flight times. The electronic system used for measuring the time of flight of the neutrons and gamrna-rays over the fixed flight path is described. The materials studied in this work were Lithium and Lead because of their importance as fuel breeding and shielding materials in conceptual fusion reactor designs. Several sample thicknesses were studied to determine the multiple scattering effects. The observed gamma-ray spectra from each sample at several scattering angles in the angular range Oº - 90° enabled absolute differential gamma-ray production cross-sections and angular distributions of the resolved gamma-rays from Lithium to be measured and compared with published data. For the Lead sample, the absolute differential gamma-ray production cross-sections for discrete 1 MeV ranges and the angular distributions were measured. The measured angular distributions of the present work and those on Iron from previous work are compared to the predictions of the Monte Carlo programme M.O.R.S.E. Good agreement was obtained between the experimental results and the theoretical predictions. In addition an empirical relation has been constructed which describes the multiple scattering effects by a single parameter and is capable of predicting the gamma-ray production cross-sections for the materials to an accuracy of ± 25%.

Spectra of modular and small-world matrices

We compute spectra of symmetric random matrices describing graphs with general modular structure and arbitrary inter- and intra-module degree distributions, subject only to the constraint of finite mean connectivities. We also evaluate spectra of a certain class of small-world matrices generated from random graphs by introducing shortcuts via additional random connectivity components. Both adjacency matrices and the associated graph Laplacians are investigated. For the Laplacians, we find Lifshitz-type singular behaviour of the spectral density in a localized region of small |?| values. In the case of modular networks, we can identify contributions of local densities of state from individual modules. For small-world networks, we find that the introduction of short cuts can lead to the creation of satellite bands outside the central band of extended states, exhibiting only localized states in the band gaps. Results for the ensemble in the thermodynamic limit are in excellent agreement with those obtained via a cavity approach for large finite single instances, and with direct diagonalization results.

Spontanoeusly resolved macroaneurysm associated with a congenital anomalous retinal artery

Purpose: To report the outcome of retinal artery macroaneurysm associated with a congenital anomalous retinal artery. Methods: The patient was examined with ophthalmoscopy and fluorescein angiography. Results: A 60-year-old woman presented with visual acuity of 20/80 in her right eye. She was found to have an abnormal retinal vessel emerging from the optic disk, passing toward the center of the macula, and looping back toward the disk. The center of the loop had a leaking macroaneurysm, which was treated conservatively. At the 4-month follow-up visit, the visual acuity in the right eye had improved to 20/20 with resolution of most of the macular edema, exudates, and hemorrhage. Conclusion: This case demonstrates that retinal artery macroaneurysm can be successfully managed with a conservative approach, even when associated with a congenital anomalous retinal vessel.