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This thesis is concerned with attempts to establish solid-state NMR as a complementary technique to X-ray crystallography for providing information on crystal structure, i.e. information regarding conformation, packing and inter- or intra-molecular interactions. Methods of assigning the solid-state NMR spectrum have been used which rely upon (^1)H-(^13)C dipolar interactions and upon the shielding anisotropy experienced by the nuclei. Single pulse experiments have also been used to identify solvate molecules. Of particular importance, the anisotropy and asymmetry have been found for a number of steroids, and the values used to assign the high frequency region of the spectrum. This has enabled chemical shifts to be linked to the hydrogen bonds that are present. Thus, the mode of hydrogen bonding can be predicted in forms of cortisone acetate for which the crystal structure is not available. Chemical shifts have also been linked with the conformation of the D ring. In this way, important crystallographic information has been gleaned from the solid-state NMR spectrum. The effect of the formation of hydrogen bonds upon the shielding tensor components of carbonyl and ester carbons has been studied, and found to cause a high frequency shift in δ22, which is probably oriented along the C=0 bonds. This leads to a high frequency shift in the isotropic chemical shift. The effect of the spinning speed upon the centreband intensity of a peak as the anisotropy and asymmetry are varied has been investigated. It has been found that at low spiiming speeds, the centreband intensity does not vary in a simple fashion. Thus it is recommended that full shielding tensor analysis is performed. The effect of the spinning speed on the sample temperature has also been studied. Results show that at low spinning speeds (up to 2 kHz) there is sample cooling as the spinning speed increases (attributed to the Joule -Thompson effect). But at higher spinning speeds (above 2 kHz) then there is sample heating as the spinning speed increases. The importance of this result is discussed. The effect of quadrupolar nuclei (35C1 and (^14)N) upon the spectrum of a spin-(^1)(_2) nucleus ((^13)C) has been studied. In favourable cases, the anisotropy in the spin-spin coupling constant has been found, whilst in other cases, the sign and magnitude of the quadrupolar coupling constant have been obtained. The broadening of resonances of carbon atoms adjacent to quadrupolar nuclei has been valuable in assigning the solid-state NMR spectra. The broadening effect has also been observed at more distant sites. It has not been possible to distinguish the effects of (^37)C1 and (^35)C1 on the carbon spectra of chlorine containing steroids.

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BACKGROUND: Adhesive capsulitis is an idiopathic disorder of the shoulder that is characterized by pain in combination with the gradual loss of passive and active range of motion. It is typically self-limiting, although the disease still remains poorly understood. However, there are several treatment modalities, both conservative and surgical, that provide significant clinical benefit for patients with adhesive capsulitis. Corticosteroid injections are an established conservative treatment method for adhesive capsulitis. Several studies have demonstrated that injections provide short-term benefits in terms of shoulder mobility and pain reduction. The intra-articular injections can be performed blindly (landmark) or with ultrasound (US) guidance. Physicians administer injections under US guidance in an attempt to improve the accuracy of the injection. However, it remains unclear whether US-guided injections relieve symptoms of adhesive capsulitis more effectively than landmark injections. OBJECTIVE: To compare the pain relief, self-reported function, and shoulder range of motion (ROM) outcomes of landmark versus US-guided corticosteroid injections for adhesive capsulitis. Methods: A total of 21 patients with adhesive capsulitis were randomized to receive either a landmark or US-guided intra-articular corticosteroid injection. Clinical outcome measures were documented at baseline, 6 weeks, and 12 weeks. These measures included a visual analog scale (VAS) for pain, the Single Assessment Numeric Evaluation (SANE) score for self-reported function, and passive shoulder ROM, including forward flexion, external rotation, and abduction. RESULTS: Both US-guided and landmark glenohumeral (GH) joint injections significantly improved VAS scores, SANE scores, and shoulder ROM outcomes. Improvement was maintained for all outcome measures in both groups throughout the 12 week treatment period. However, there were no significant differences seen in outcome measures between the two groups except that US-guided provided greater improvement in abduction at the 6 week follow-up (P = .004). CONCLUSIONS: This preliminary report found that there is no significant difference in the effectiveness of US-guided and landmark cortisone injection in terms of pain improvement, self-reported functions, and ROM outcomes for adhesive capsulitis.

In our study, we analyzed four stress markers (cortisol, cortisone, DHEA and DHEAS) in blood serum in young sows using minimally invasive heart catheterisation as the stress factor. The marker levels were assessed in four defined periods of the experiment, beginning with the baseline level on the day before intervention (1), the second period was after the introduction of anaesthesia (2), the third was after conducting tissue stimulation or ablation (3), and the final period was after the end of the catheterisation (4). Cortisol and cortisone were detected using HPLC method, DHEA(S) by commercial kits. For statistical analyses non-parametric tests were used (due to non standard Gaussian data distribution). In our study we arranged these experiments: 1. Diurnal variability in these markers concentration during heart catheterisation was tested. 2. Are there differences between stress markers concentration the day before experiment (sampling 1) and in the day of the catheterisation (samplings 2, 3, 4)? 3. Are there differences between these markers concentration during operation (the first sampling was excluded)? 4. The cortisol/cortisone ratio was calculated. We found only minimal statistical differences in studied markers between the morning and afternoon group (p > 0.05) in experiment 1. For tested...