New techniques for quantifying distributions of J couplings and phosphate chains lengths have been developed using a combination of theoretical calculations, numerical simulations and NMR experiments on a cadmium phosphate glass x(CdO)-(1-x)(P205) (x=57.5 mol%). In addition, the effect of ageing and a novel sol-gel preparation route have been investigated in sodium borophosphate glasses.

No description available.

The work described in this thesis is based on the use of multinuclear NMR and protein crystallography as two powerful and symbiotic biological structural tools to study the catalytic mechanisms of five phosphoryl transfer enzymes: β-phosphoglucomutase, phosphoserine phosphatase, cAMP-dependent protein kinase, small G protein RhoA- RhoGAP, and UMP/CMP kinase. The central feature is the use of magnesium and aluminium fluorides as transition state analogues for phosphoryl group transfer. β-Phosphoglucomutase is first examined using stable βG1P phosphonate analogues of which (S)-βCHFG1P and βCH2G1P form MgF3– and AlF4– TSA complexes with βPGMwt. Next, mutant studies show D10N and D8E form AlF4– complexes while D8N does not. Only D10N forms a fluoroberyllate complex on the nucleophilic Asp 8, which can also be phosphorylated by acetyl phosphate. The general acid-base role of D13 in PSP is further established by showing the inactivity of PSPD13N, a mutant that forms MgF3– and AlF4– TSA complexes with water but not serine. Fundamental functional differences between PSP and βPGM are rationalised. cAPK forms MgF3– and AlF4– TSA complexes, disproving the 'AlF30' assignment in PDB: 1L3R. The binding constant of cAPK for its MgF3– TSA is only ~10 fold weaker than for the AlF4– TSA complex. This suggests that fluoride inhibition of a wide range of signalling proteins may be dominated by MgF3– rather than by the more widely studied AlF4– with significant physiological implications. 19F NMR data confirm the RhoA-GDP-MgF3–-OH2-RhoGAP TSA solid state structure, and identify an AlF4– TSA complex that obeys the Charge Balance Hypothesis. A GAP-free octahedral RhoA-GDP-AlF3(H2O)0 complex is formed that also conforms to the CBH. NMR and crystallography show RhoA-GDP-MgF3–-RhoGAPR85A and RhoA-GDP-AlF4–-RhoGAPR85A TSA complexes maintain negative charge on the metal fluoride moieties via Tyr 34 coodination. Finally, substrate analogue GTPγF is remarkably stable to hydrolytic acitivity by RhoA alone, or with RhoGAP with or minus its arginine finger. 19F NMR data disprove the earlier assignment of tbp 'AlF30' in UMP/CMP kinase structures crystallised at pH 8.5 and show MgF3– is the actual TSA at high pH. NMR/pH titration reveals a new intermediate aluminium TSA species, AlF3Z, not hitherto identified. NMR analysis endorses earlier solid state observations on a UMPK-ADP-BeF2 0-UDP TSA complex and demonstrates the catalytic promiscuity of UMPKdicty. AMPCP is a stable substitute for ADP in TSA complex formation while AMPCF2P or ADPβF fail unexpectedly. Similarly, UMP cannot be replaced by 5FdUMP. This thesis is a prime example of the symbiotic use of 19F NMR and protein crystallography to study enzyme mechanisms. 19F NMR can identify TSA complex formation in solution and hence can direct crystal trials. Crystal structures are more accurately assigned using NMR data while, in turn, they give further support to detailed interpretation of NMR signals.

Measurement of enhancements to the nuclear magnetic spin-lattice relaxation times of solvent water protons were used to probe the complexation of manganese(II) ions with the iron protein of nitrogenase. Enhancement data were used to determine concentrations of bound manganese in solutions containing the metal ions and buffered aqueous protein, and these concentration data treated by the Scatchard plot method to provide binding parameters for the manganese-protein complex. These studies showed four independent, equivalent sites on the protein for binding manganese ions. Competition studies in solutions containing the iron protein and known concentrations of manganese(II) and magnesium(II) ions showed that the four sites available to manganese could alternatively bind magnesium ions.

Many chemically important nuclei are quadrupolar with half-integer spin (i.e., spin I = 1.5, 2.5, etc.) The presence of quadrupolar broadening for such nuclei can limit the information that may be extracted using NMR. MAS is able to remove first-order quadrupolar broadening but can only reduce the second-order contribution to the linewidth. The MQMAS and STMAS techniques have enabled high-resolution NMR spectra of half-integer quadrupolar nuclei in the solid state to be obtained by two-dimensional correlation under MAS conditions. Both of these experiments have several well-known limitations. One is that the conversion pulses in particular are very inefficient and the other is that the longer acquisition times required for two-dimensional experiments can be a limiting factor. Both of these disadvantages are addressed in this thesis. For the former case, existing composite pulse schemes designed to improve the efficiency of the conversion of multiple-quantum coherences are compared using 27Al and 87Rb MQMAS NMR of a series of crystalline and amorphous materials. In the latter case, a new experiment, named STARTMAS, is introduced that enables isotropic spectra of spin I = 1.5 spectra to be acquired in real time. The theoretical basis of the technique is explained and its applicability demonstrated using 23Na and 87Rb NMR of a wide range of solids. The nuclear Overhauser effect (NOE) is one of the most widely exploited phenomena in NMR and is now widely used for molecular structure determination in solution. NOEs in the solid state are rare and those to quadrupolar nuclei rarer still, this being due to the general absence of motion on the correct timescale and the usual efficiency of quadrupolar T1 relaxation, respectively. In this thesis, 11B{1H} transient NOE results are presented for a range of solid borane adducts. A comparison is made of the 11B NMR enhancements observed under MAS and static conditions and a rationale is proposed for the behaviour in the latter case.

No description available.

The main focus of this thesis is the investigation of structure and motion of different materials by applying different solid-state NMR techniques. In the first section (1) some of the bases of NMR are described both in a Classical (1.1) and Quantum Mechanical (1.2) approach, while the next two sections deal with the experimental part of the work. In section 2 solid-state NMR studies of CsC60 are described and an unambiguous assignment of the 13C NMR spectrum of the polymer phase of CsC60, which is based solely on our experimental data, is presented. In contrast to previous work, the assignment does not rely on the knowledge of the electronic structure of this material and our results support a fully three-dimensional electronic structure as opposed to a quasi one-dimensional one. This is achieved using a two-dimensional 13C MAS NMR correlation experiment, which identifies nuclei coupled via a through-bond scalar interaction, the Refocused INADEQUATE. In section 3 solid-state NMR experiments performed on polyethylene and long-chain n-alkanes corresponding to the formula C246H494 are described. Particular attention is given to some specific issues such as chain folding and a detailed study of the saturation-recovery curves (T1) obtained is carried out for different materials. The model elaborated is able to simulate all the data recorded and the presence of an interphase between the crystalline and the amorphous parts of the samples is proposed. To help the understanding of the structure and the motion of long-chain n-alkanes in section 3 some deuterated samples such as C216H434-d24 and C12H25(CH2)192CHDC11D23+C162H326 ("the mixture") are also studied. Deuterium NMR is widely used and we fit all the experimental line shape of the different samples at different temperatures. Diverse models for the structure and motion of such materials are given, which take into account all the experimental results obtained.

Τα ομοιώματα παίζουν σημαντικό ρόλο στην εξασφάλιση της σωστής λειτουργίας των συστημάτων μαγνητικού συντονισμού. Eιδικά όταν εφαρμόζονται μέθοδοι μέτρησης των χρόνων μαγνητικής αποκατάστασης (ποσοτική ΜRI), όπου οι ρυθμίσεις του μετρητικού οργάνου έχουν σοβαρότατο αντίκτυπο στις μετρούμενες τιμές, είναι απαραίτητη η χρήση μιας σειράς κατάλληλων ομοιωμάτων που θα λειτουργούν ως πρότυπα βαθμονόμησης των οργάνων μέτρησης. Ένα ομοίωμα προσομοίωσης χρόνων μαγνητικής αποκατάστασης θα πρέπει να έχει ορισμένα χαρακτηριστικά, μεταξύ των οποίων χρόνους μαγνητικής αποκατάστασης παρόμοιους με αυτούς των ανθρώπινων ιστών και χημική και φυσική σταθερότητα στο χρόνο. Σε αυτή την εργασία παρασκευάστηκε ένα υλικό αποτελούμενο από διαφορετικές συγκεντρώσεις ζελατίνης και Gd-DTPA, μελετήθηκαν οι χρόνοι μαγνητικής αποκατάστασης του υλικού αναλόγως με την συγκέντρωση των συστατικών του και αξιολογήθηκε η σταθερότητά του. Παρατηρήθηκε πως η αύξηση της συγκέντρωσης της ζελατίνης προκαλούσε έντονη μείωση του Τ1 και του Τ2. Η αύξηση της συγκέντρωσης της παραμαγνητικής ουσίας προκαλούσε έντονη μείωση του Τ1 και μικρότερη μείωση του Τ2, η οποία ήταν πιο αισθητή σε χαμηλές συγκεντρώσεις ζελατίνης. Τα διαλύματα που παρασκευάστηκαν παρουσίασαν μεγάλο εύρος τιμών Τ1 και Τ2, εντός του οποίου περιλαμβάνονται οι τιμές που απαντώνται στους ανθρώπινους ιστούς. Ο λόγος όμως Τ1/Τ2 των σημαντικότερων ιστών δεν επιτεύχθηκε σε κανένα από τα διαλύματα. Τα διαλύματα χωρίς παραμαγνητική ουσία ήταν σχετικά σταθερά ως προς την Τ1 , ενώ η Τ2 παρουσιάζε μια μικρή σταδιακή μείωση στο χρόνο. Τα διαλύματα με χαμηλή συγκέντρωση ζελατίνης παρουσία οποιασδήποτε συγκεντρώσεως παραμαγνητικής ουσίας εμφάνισαν σταθερές τιμές των Τ1 και Τ2 καθ’ όλη τη διάρκεια της μελέτης, με μικρές διακυμάνσεις στις διαδοχικές μετρήσεις. Τα διαλύματα με υψηλή συγκέντρωση ζελατίνης εμφάνισαν μια πτώση των τιμών τόσο της Τ1 όσο και της Τ2 στις πρώτες 6 μετρήσεις (2 μήνες), ενώ στη συνέχεια οι τιμές σταθεροποιήθηκαν. Συμπερασματικά, είναι δυνατή η παρασκευή υλικών που προσομοιάζουν τους ανθρώπινους ιστούς ως προς τους χρόνους μαγνητικής αποκατάστασης χρησιμοποιώντας απλά και οικονομικά συστατικά. Το υλικό το οποίο δοκιμάστηκε επιδέχεται βελτιώσεις μέσω της προσθήκης σταθεροποιητικών παραγόντων και κάποιου συστατικού που να επιδρά κυρίως στον Τ2. / -

In this work, multinuclear solid-state nuclear magnetic resonance (NMR) spectroscopy is used to investigate a range of inorganic materials, often in combination with DFT (density functional theory) studies. Solid-state NMR is particularly suited to the study of aluminophosphates (AlPOs), as the basic components of their frameworks have NMR active isotopes (²⁷Al, ³¹P, ¹⁷O), as do many of the atoms that comprise the structure directing agent (¹³C, ¹H, ¹⁵N), and the charge-balancing anions (OH⁻, F⁻). A study of the AlPO STA-15 (St Andrews microporous solid-15) provides an introduction to using solid-state NMR spectroscopy to investigate AlPOs. More in-depth studies of AlPO STA-2 (St Andrews microporous solid-2) and MgAPO STA-2 (magnesium-substituted AlPO) examine charge-balancing mechanisms in AlPO-based materials. A range of scandium carboxylate metal-organic frameworks (MOFs), with rigid and flexible frameworks, have been characterised by multinuclear solid-state NMR spectroscopy (⁴⁵Sc, ¹³C and ¹H). The materials studied contain a variety of metal units and organic linkers. ¹³C and ¹H magic-angle spinning (MAS) NMR were used to study the organic linker molecules and ⁴⁵Sc MAS NMR was used to study the scandium environment in the MOFs Sc₂BDC₃ (BDC = 1,4-benzenedicarboxylate), MIL-53(Sc), MIL-88(Sc), MIL-100(Sc) and Sc-ABTC (ABTC = 3,3`,5,5`-azobenzenetetracarboxylate). Functionalised derivatives of Sc₂BDC₃ and MIL-53(Sc) were also studied. The ⁴⁵Sc MAS NMR spectra are found to be strongly dependant on the Sc³⁺ coordination environment. ²⁷Al and ²⁵Mg MAS NMR have been used to study Ti-bearing hibonite samples (of general formula Ca(Al, Ti, Mg)₁₂O₁₉), and results compared to a recent complementary neutron powder diffraction study, in order to investigate the substitution sites for Ti³⁺/⁴⁺ and Mg²⁺. A DFT investigation was also carried out on the aluminium end member, CaAl₁₂O₁₉, due to debate in the literature on the ²⁷Al NMR parameters for the trigonal-bipyramidal site. The substitution of Mg onto the tetrahedral site (M3) and Ti primarily onto one of the octahedral sites (M4) is supported.

Dynamic nuclear polarisation is a technique that allows one to increase the signal-to-noise ratio in an NMR experiment substantially, by transferring the inherently larger electron polarisation to the nuclei. Quantum mechanical models of this effect have thus far been limited to the description of only a few nuclei. This is due to the exponential scaling of the matrices involved in the description of the system. In this thesis methods of reducing the state space needed to accurately describe the simulation of solid effect DNP were explored and tested. Krylov Bogoliubov averaging has been used to remove high frequency oscillations from the system Hamiltonian and confine the trajectory of the dynamics to the zero quantum coherence subspace. Truncation of the basis spanning the Liouville space to low spin correlation orders has been tested and a condition for a minimum truncation level was found. A strategy based on a projection method, which allows one to describe the spin polarisation transient with multi-exponential functions, is introduced. This results in a linear scaling of the propagator with the number of spins. The influence of the parameters involved in the solid effect on the dynamics of the polarisation build up is discussed. The second part of this thesis is concerned with a novel approach to detecting fast molecular dynamics with the use of multiple RF receive and transmit coils. A proof of principle probe with two decoupled RF coils is presented, as well as a field map based shimming strategy and fast 2D data acquired with the probe. Lastly a probe with six RF coils, based on the design of the dual coil probe, will be presented, and initial data shown. The potential for using this probe in hyper-polarisation experiments for protein binding and folding studies will be discussed.