True chemical shift correlation maps:a TOCSY experiment with pure shifts in both dimensions

Signal resolution in H NMR is limited primarily by multiplet structure. Recent advances in pure shift NMR, in which the effects of homonuclear couplings are suppressed, have allowed this limitation to be circumvented in 1D NMR, gaining almost an order of magnitude in spectral resolution. Here for the first time an experiment is demonstrated that suppresses multiplet structure in both domains of a homonuclear two-dimensional spectrum. The principle is demonstrated for the TOCSY experiment, generating a chemical shift correlation map in which a single peak is seen for each coupled relationship, but the principle is general and readily extensible to other homonuclear correlation experiments. Such spectra greatly simplify manual spectral analysis and should be well-suited to automated methods for structure elucidation. © 2010 American Chemical Society.

Spatially-multiplexed fibre-optic Bragg grating strain and temperature sensor system based on interferometric wavelength-shift detection

A prototype fibre-optic system using interferometric wavelength-shift detection, capable of multiplexing up to 32 fibre-optic Bragg grating strain and temperature sensors with identical characteristics, has been demonstrated. This system is based on a spatially multiplexed scheme for use with fibre-based low-coherence interferometric sensors, reported previously. Four fibre-optic Bragg grating channels using the same fibre grating have been demonstrated for measuring quasi-static strain and temperature.

Optical in-fiber Bragg grating sensor systems for medical applications

Two in-fiber Bragg grating (FBG) temperature sensor systems for medical applications are demonstrated: (1) an FBG flow-directed thermodilution catheter based on interferometric detection of wavelength shift that is used for cardiac monitoring; and (2) an FBG sensor system with a tunable Fabry-Perot filter for in vivo temperature profiling in nuclear magnetic resonance (NMR) machines. Preliminary results show that the FBG sensor is in good agreement with electrical sensors that are widely used in practice. A field test shows that the FBG sensor system is suitable for in situ temperature profiling in NMR machines for medical applications.

Data transmission by frequency-hopped multilevel frequency shift keying

Spread spectrum systems make use of radio frequency bandwidths which far exceed the minimum bandwidth necessary to transmit the basic message information.These systems are designed to provide satisfactory communication of the message information under difficult transmission conditions. Frequency-hopped multilevel frequency shift keying (FH-MFSK) is one of the many techniques used in spread spectrum systems. It is a combination of frequency hopping and time hopping. In this system many users share a common frequency band using code division multiplexing. Each user is assigned an address and the message is modulated into the address. The receiver, knowing the address, decodes the received signal and extracts the message. This technique is suggested for digital mobile telephony. This thesis is concerned with an investigation of the possibility of utilising FH-MFSK for data transmission corrupted by additive white gaussian noise (A.W.G.N.). Work related to FH-MFSK has so far been mostly confined to its validity, and its performance in the presence of A.W.G.N. has not been reported before. An experimental system was therefore constructed which utilised combined hardware and software and operated under the supervision of a microprocessor system. The experimental system was used to develop an error-rate model for the system under investigation. The performance of FH-MFSK for data transmission was established in the presence of A.W.G.N. and with deleted and delayed sample effects. Its capability for multiuser applications was determined theoretically. The results show that FH-MFSK is a suitable technique for data transmission in the presence of A.W.G.N.

Influence of check and field size on the visual evoked magnetic response to a pattern shift stimulus

A decrease in the check size of a pattern shift stimulus increases the latency and amplitude of the visual evoked potential (VEP) P100. In addition, for a given check size, decreasing the size of the stimulus field increases the latency and amplitude of the P100. These results imply that the central regions of the retina make a significant contribution to the generation of the electrical P100. However, the corresponding magnetic P100m may have a different origin. We have studied the effects of check and field size on the P100m in five normal subjects using a DC-Squid, second-order gradiometer. Magnetic responses were recorded at the positive maximum of the P100m over the occipital scalp to six check sizes (10-100') presented in a large (13 degrees 34') and small (5 degrees 14') field and to a large check (100') presented in seven field sizes (1 degree 45' - 15 degrees 10'). No responses were recorded to any check size with a small field. Decreasing the check size presented in a large field increased latency of the P100m by approx. 30 ms while the amplitude of the response decreased with the largest reduction occurring between 70' and 12' checks. Using a large check, latency increased and amplitude decreased as the field size was reduced. The latency changes in response to check and field size were similar to those described for the VEP although the magnitudes of the magnetic changes were greater. Unlike the VEP, amplitude responses were maximal when large checks were presented in a large stimulus field. This suggests that regions outside the central retina make a more significant contribution to the visual evoked magnetic response than they do to the VEP, and that the P100m may be useful clinically in the study of diseases that affect the more peripheral regions of the retina.

Topography of visual evoked magnetic responses to pattern shift, pattern onset and flash stimuli

Different visual stimuli may activate separate channels in the visual system and produce magnetic responses from the human bran which originate from distinct regions of the visual cortex. To test this hypothesis, we have investigated the distribution of visual evoked magnetic responses to three distinct visual stimuli over the occipital region of the scalp with a DC-SQUID second-order gradiometer in an ubshielded environment. Patterned stimuli were presented full field and to the right half field, while a flash stimulus was presented full field only, in five normal subjects. Magnetic responses were recorded from 20 to 42 positions over the occipital scalp. Topographic maps were prepared of the major positive component within the first 150ms to the three stimuli, i.e., the P100m (pattern shift), C11m (pattern onset) and P2m (flash). For the pattern shift stimulus the data suggested the source of the P100m was close to the midline with the current directed towards the medial surface. The data for the pattern onset C11m suggested a source at a similar depth but with the current directed away from the midline towards the lateral surface. The flash P2m appeared to originate closer to the surface of the occipital pole than both the patterned stimuli. Hence the pattern shift (which may represent movement), and the pattern onset C11m (representing contrast and contour) appear to originate in similar areas of brain but to represent different asepcts of cortical processing. By contrast, the flash P2m (representing luminance change) appears to originate in a distinct area of visual cortex closer to the occipital pole.

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.

Design and construction of an ultrasonic probe for use in a Cryo-Magnet NMR Spectrometer

SINNMR (Sonically Induced Narrowing of the Nuclear Magnetic Resonance spectra of solids), is a novel technique that is being developed to enable the routine study of solids by nuclear magnetic resonance spectroscopy. SINNMR aims to narrow the broad resonances that are characteristic of solid state NMR by inducing rapid incoherent motion of solid particles suspended in a support medium, using high frequency ultrasound in the range 2-10 MHz. The width of the normal broad resonances from solids are due to incomplete averaging of several components of the total spin Hamiltonian caused by restrictions placed on molecular motion within a solid. At present Magic Angle Spinning (MAS) NMR is the classical solid state technique used to reduce line broadening, but: this has associated problems, not least of which is the appearance of many spinning side bands which confuse the spectra. It is hoped that SlNNMR will offer a simple alternative, particularly as it does not reveal spinning sidebands The fundamental question concerning whether the use of ultrasound within a cryo-magnet will cause quenching has been investigated with success, as even under the most extreme conditions of power, frequency and irradiator time, the magnet does not quench. The objective of this work is to design and construct a SINNMR probe for use in a super conducting cryo-magnet NMR spectrometer. A cell for such a probe has been constructed and incorporated into an adapted high resolution broadband probe. It has been proved that the cell is capable of causing cavitation, up to 10 MHz, by running a series of ultrasonic reactions within it and observing the reaction products. It was found that the ultrasound was causing the sample to be heated to unacceptable temperatures and this necessitated the incorporation of temperature stabilisation devices. Work has been performed on the investigation of the narrowing of the solid state 23Na spectrum of tri-sodium phosphate using high frequency ultrasound. Work has also been completed on the signal enhancement and T1 reduction of a liquid mixture and a pure compound using ultrasound. Some preliminary "bench" experiments have been completed on a novel ultrasonic device designed to help minimise sample heating. The concept involves passing the ultrasound through a temperature stabilised, liquid filled funnel that has a drum skin on the end that will enable the passage of ultrasound into the sample. Bench experiments have proved that acoustic attenuation is low and that cavitation in the liquid beyond the device is still possible.

The synthesis of a ferromagnetic polymer

The aim of this study was to prepare a ferromagnetic polymer using the design elements of molecular magnets. This involved the preparation of co-polyradicals of phenylacetylenes bearing nitronyl nitroxides and nitro/cyano groups. The magnetic properties of the materials were determined using a SQUID magnetometer. A novel rhodium catalyst, Rh(NBD)(NH3)Cl, was prepared in order to obtain good yields of polymerisation. A wide range of substituted phenylacetylenes were first homopolymerised in order to assess the efficiency of the catalyst. Yields were generally high, between 75% and 98%, and the time of polymerisation was short (one hour). SEC analysis revealed that the Mw of the polymers were in the range of 200,000 and 250,000. The discovery that phenylboronic acid acts a co-catalyst for the polymerisation served to increase the yields by 10% to 20% but the Mw of the polymers was reduced to approximately 100,000. Co-polyradicals were prepared in good to excellent yield using the new catalyst. The magnetic properties in the temperature range of 300K to 1.8K were investigated by SQUID, which revealed a spin glass system, antiferromagnets and possible dipolar magnets. Short-range ferromagnetic interactions between 300K and 100K were found in a co-polyradical containing nitronyl nitroxide and cyano substituted monomers. The magnetic properties were dependent upon both the type of monomers utilised and the ratio between them. The effects of ring substituents on the terminal alkyne have been studied by carbon-13 NMR. There was no correlation however, between the chemical shift of terminal alkyne and the polymerisability of the monomer.

Development of novel NMR pulse sequences

To elucidate the structures of orgamc molecules in solution using pulse FT NMR, heteronuclear pulse sequence experiments to probe carbon-13 (13C) and proton (1H) spin systems are invaluable. The one-dimensional insensitive nucleus detected PENDANT experiment finds popular use for structure determination via one-bond 13C-1H scalar couplings. PENDANT facilitates the desired increase in 13C signal-to-noise ratio, and unlike many other pulse sequence experiments (e.g., refocused INEPT and DEPT), allows the simultaneous detection of 13C quaternary nuclei. The tlrst chapter herein details the characterisation of PENDANT and the successful rectification of spectral anomalies that occur when it is used without proton broadband decoupling. Multiple-bond (long-range) l3C-1H scalar coupling correlations can yield important bonding information. When the molecule under scrutiny is devoid of proton spectral crowding, and more sensitive 'inverse' pulse sequence experiments are not available, one may use insensitive nucleus detected long-range selective one-dimensional correlation methods, rather than more time consuming and insensitive multidimensional analogues. To this end a novel long-range selective one-dimensional correlation pulse sequence experiment has been invented. Based on PENDANT, the new experiment is shown to rival the popular selective INEPT technique because it can determine the same correlations while simultaneously detecting isolated 13C quaternary nuclei. INEPT cannot facilitate this, potentially leaving other important quaternary nuclei undetected. The novel sequence has been modified further to yield a second novel experiment that simultaneously yields selective 13C transient nOe data. Consequently, the need to perform the two experiments back-to-back is conveniently removed, and the experimental time reduced. Finally, the SNARE pulse sequence was further developed. SNARE facilitates the reduction of experimental time by accelerating the relaxation of protons upon which pulse sequences, to which SNARE is appended, relies. It is shown, contrary to the original publication, that reiaxation time savings can be derived from negative nOes.

NMR spectroscopy in the presence of ultrasound and other perturbations

The work described in this thesis has been concerned with exploring the potential uses of ultrasound in Nuclear Magnetic Resonance (NMR) spectroscopy, The NMR spectra of liquids provide detailed structural information that may be deduced from the chemical shifts and spin-spin coupling, that are evident in the narrow resonances, arising from some of the nuclear broadening interactions being reduced to zero. In the solid state, all of the nuclear broadening interactions are present and broad lines in the NMR spectrum are observed. Current techniques employed to reduce the line widths in solids are based on coherent averaging techniques such as MAS NMR1,2 which can remove first order interactions. Recently DOR3 and DAS4 have become available to remove higher order interactions. SINNMR (Sonically Induced Narrowing of the NMR spectra of solids) has been reported by Homer et al5 and developed by Homer and Howard6 to reduce the line widths of solids. The basis of their work is the proposal that a colloidal suspension of solid particles can be made to move like large molecules by using ultrasonic agitation. The advantage of the technique is that the particles move incoherently removing all of the nuclear interactions responsible for broad lines. This thesis describes work on the extension of SINNMR by showing that the line width of 27AI and 11B for the glass Na20/B203/AI203 can be reduced by placing solid particles in a colloidal suspension. Further line width reduction is possible by applying ultrasound, at 2 MHz, of sufficient intensity. It is proposed that a cavitation field is responsible for imparting sufficient rotational motion to the solid particles to partially average the nuclear interactions responsible for broad lines. Rapid stirring of the colloidal suspension generates turbulent flow, however, the motion is insufficient to narrow the line widths for 27AI in the glass. Investigations of sonochemical reactions for in situ rate measurements by NMR have been made. 8y using the Weissler reaction7, it has been shown that ultrasonic cavitation is possible up to 10MHz. Preliminary studies have been carried out into the rate of ultrasonic polymerisation of methylmethacrylate by NMR. Long range order in liquid crystals can imposed when they are aligned in the presence a magnetic field. The degree of alignment can be monitored by NMR using, for example a deuterated solute added to the liquid crystal8. Ultrasonic streaming can then be employed to deflect the directors of the liquid crystal from their equilibrium position, resulting in a change In the NMR spectrum. The angle of deflection has been found for the thermotropic liquid crystal (I35) to be ca, 35° and for the lyotropic (ZLI-1167) to be ca, 20°, Mechanical stirring can used to re- orientate the liquid crystal but was found to give a smaller deflection, In a separate study, that did not use ultrasound, it has been found that the signal to noise ratio of 13C NMR signals can be enhanced by rapidly stirring a Iiquid. Accelerating the diffusion of nuclei out of the coil region enables M0 to be re-established more rapidly than the normal relaxation process. This allows the pulse repetition rate to be reduced without saturating the spin system. The influence of varying the relaxation delay, acquisition time and inter-pulse delay have been studied and parameters optimised. By studying cholesterol the technique was found to be most effective for nuclei with long relaxation times, such as quaternary carbon sites. Key Worde: NMR, Ulf.rasciund, 1,.lqi.fi!:l cryllltalt!h SCll1C1otlemlstryl I!r1hano~d algnflllf

The development and applications of the combined use of NMR and ultrasound

The objective of the research carried out in this report was to observe the first ever in-situ sonochemical reaction in the NMR Spectrometer in the megahertz region of ultrasound. Several reactions were investigated as potential systems for a sonochemical reaction followed by NMR spectroscopy. The primary problem to resolve when applying ultrasound to a chemical reaction is that of heating. Ultrasound causes the liquid to move and produces 'hot spots' resulting in an increase in sample temperature. The problem was confronted by producing a device that would counteract this effect and so remove the need to account for heating. However, the design of the device limited the length of time during which it would function. Longer reaction times were required to enable observations to be carried out in the NMR spectrometer. The fIrst and most obvious reactions attempted were those of the well-known ultrasonic dosimeter. Such a reaction would, theoretically, enable the author to simultaneously observe a reaction and determine the exact power entering the system for direct comparison of results. Unfortunately, in order to monitor the reactions in the NMR spectrometer the reactant concentrations had to be signifIcantly increased, which resulted in a notable increase in reaction time, making the experiment too lengthy to follow in the time allocated. The Diels-Alder Reaction is probably one of the most highly investigated reaction systems in the field of chemistry and it was this to which the author turned her attention. Previous authors have carried out ultrasonic investigations, with considerable success, for the reaction of anthracene with maleic anhydride. It was this reaction in particular that was next attempted. The first ever sonochemically enhanced reaction using a frequency of ultrasound in the megahertz (MHz) region was successfully carried out as bench experiments. Due to the complexity of the component reactants the product would precipitate from the solution and because the reaction could only be monitored by its formation, it was not possible to observe the reaction in the NMR spectrometer. The solvolysis of 2-chloro-2-methylpropane was examined in various solvent systems; the most suitable of which was determined to be aqueous 2-methylpropan-2-ol. The experiment was successfully enhanced by the application of ultrasound and monitored in-situ in the NMR spectrometer. The increase in product formation of an ultrasonic reaction over that of a traditional thermal reaction occurred. A range of 1.4 to 2.9 fold improvement was noted, dependent upon the reaction conditions investigated. An investigation into the effect of sonication upon a large biological molecule, in this case aqueous lysozyme, was carried out. An easily observed effect upon the sample was noted but no explanation for the observed effects could be established.

Solvent induced NMR chemical shifts that arise from molecular encounters

Recently Homer and Percival have postulated that intermolecular van der Waals dispersion forces can be characterized by three mechanisms. The first arises via the mean square reaction field < R1; 2> due to the transient dipole of a particular solute molecule that is considered situated in a cavity surrounded by solvent molecules; this was characterized by an extended Onsager approach. The second stems from the extra cavity mean square reaction field < R2; 2> of the near neighbour solvent molecules. The third originates from square field electric fields E2BI due to a newly characterized effect in which solute atoms are `buffeted' by the peripheral atoms of adjacent solvent molecules. The present work concerns more detailed studies of the buffeting screening, which is governed by sterically controlled parameter (2T - T)2, where and are geometric structural parameters. The original approach is used to characterise the buffeting shifts induced by large solvent molecules and the approach is found to be inadequate. Consequently, improved methods of calculating and are reported. Using the improved approach it is shown that buffeting is dependent on the nature of the solvent as well as the nature of the solute molecule. Detailed investigation of the buffeting component of the van der Waals chemical shifts of selected solutes in a range of solvents containing either H or Cl as peripheral atoms have enabled the determination of a theoretical acceptable value for the classical screening coefficient B for protons. 1H and 13C resonance studies of tetraethylmethane and 1H, 13C and 29Si resonance studies of TMS have been used to support the original contention that three (< R1; 2> , < R2; 2> and E2BI) components of intermolecular van der Waals dispersion fields are required to characterise vdW chemical shifts.

The use of driven equilibrium conditions in the measurement of NMR relaxation times

The further development of the use of NMR relaxation times in chemical, biological and medical research has perhaps been curtailed by the length of time these measurements often take. The DESPOT (Driven Equilibrium Single Pulse Observation of T1) method has been developed, which reduces the time required to make a T1 measurement by a factor of up to 100. The technique has been studied extensively herein and the thesis contains recommendations for its successful experimental application. Modified DESPOT type equations for use when T2 relaxation is incomplete or where off-resonance effects are thought to be significant are also presented. A recently reported application of the DESPOT technique to MR imaging gave good initial results but suffered from the fact that the images were derived from spin systems that were not driven to equilibrium. An approach which allows equilibrium to be obtained with only one non-acquisition sequence is presented herein and should prove invaluable in variable contrast imaging. A DESPOT type approach has also been successfully applied to the measurement of T1. T_1's can be measured, using this approach significantly faster than by the use of the classical method. The new method also provides a value for T1 simultaneously and therefore the technique should prove valuable in intermediate energy barrier chemical exchange studies. The method also gives rise to the possibility of obtaining simultaneous T1 and T1 MR images. The DESPOT technique depends on rapid multipulsing at nutation angles, normally less than 90^o. Work in this area has highlighted the possible time saving for spectral acquisition over the classical technique (90^o-5T_1)_n. A new method based on these principles has been developed which permits the rapid multipulsing of samples to give T_1 and M_0 ratio information. The time needed, however, is only slightly longer than would be required to determine the M_0 ratio alone using the classical technique. In ^1H decoupled ^13C spectroscopy the method also gives nOe ratio information for the individual absorptions in the spectrum.