Zugl.: Karlsruhe, Universiẗat, Diss., 2006.

A detailed row by row investigation of major lateral tooth cusp mineralisation, together with the concomitant development of the superior epithelial tissue surrounding the teeth of the chiton Acanthopleura hirtosa has been undertaken using a combination of light microscopy, and scanning and transmission electron microscopy. A holistic approach has been adopted that encompasses observations over a range of spatial scales, from whole radula mineralisation processes to those occurring within individual tooth cusps at various stages of development. In addition, mineralisation in radulae from freshly collected animals has been compared to that of animals maintained for extensive periods within a newly developed iron limited system, which restricts radula mineralisation without impeding the formation of the organic matrix. An evaluation of the iron limitation technique has revealed that maintaining specimens of A. hirtosa within an iron poor environment results in a significant departure from the normal pattern of mineralisation in these animals. As a consequence of iron limitation, there is an obvious increase in the number of unmineralised tooth rows in addition to associated alterations in structure and composition at all stages of tooth development. In normal specimens of A. hirtosa, the onset of mineralisation in the tooth cusps occurs following the prior accumulation of iron at the junction zone and the sudden accumulation of iron containing granules in the cusp epithelium at tooth row 13. The superior epithelium surrounding the tooth cusps undergoes a series of developmental changes leading up to, and following, the onset of mineralisation. In particular, the abundance of mitochondria within the apical cusp epithelium increases, presumably in order to provide the ideal conditions of pH, and thus solubility, needed for the supersaturation of iron and its nucleation at row 13. Once mineralisation has commenced, the microvilli attached to the cusps develop rapidly, and are suggested to do so in order to facilitate the transport of iron, and thereby ensure that a high concentration gradient of this element into the cusps is maintained. The delivery of iron into the cusps occurs from two fronts, the first from the superior epithelium via the posterior surface, and the second from the junction zone via an internal pathway situated along the lepidocrocite boundary between the magnetite and core regions of the tooth. The existence of a plume of elements between this internal mineralisation pathway and the junction zone, provides the first direct evidence that the junction zone is involved in the storage and release of elements for cusp mineralisation. Data from iron limited radulae also indicate that iron continues to be deposited at the junction zone in preference to the superior epithelium or cusps, despite the disruption of mineralisation, highlighting the importance of this region in the mineralisation process. Iron reinstatement experiments have also shown that the internal pathways of iron delivery within the organic matrix remain viable, despite prolonged periods of iron limitation. In addition, the reinstatement of iron has revealed that the plumes, situated between the junction zone and internal mineralising pathway of the cusp, stem from the centre of the plate like junction zone, directly above the stylus canal, a tube like cavity situated within the styli of each major lateral tooth. An in depth study of the stylus canal has revealed that cells within the canal are remarkably similar to those of the epithelium surrounding the cusps, suggesting that this structure may also be involved in the delivery of ions to the junction zone. The stylus canal is shown to be present in the major lateral tooth cusps of 38 chiton species distributed worldwide, and is therefore likely to be a feature common to all chitons. The presence of the canal, and indeed its absence from the bases of all remaining non iron mineralised teeth, irrespective of chiton species, also points strongly to a functional relationship between the stylus canal and tooth cusp mineralisation.

Regensburg, Univ., Diss., 2008

Regensburg, Univ., Diss., 2008

Univ., Diss., 2009--Kassel.

Universiẗat, Diss., 2003--Würzburg.

Universiẗat, Diss., 2004--Bielefeld.

Die Entstehung zeitlich veränderlicher kolloidaler Strukturen in wäßrigen Calciumphosphat-Dispersionen wurde abgebildet und einer Strukturanalyse unterzogen. Diese wurde durchgeführt unter Einsatz verschiedener bildgebenderund Streumethoden, deren Ergebnisse verglichen wurden. Ziel der Arbeit war es, aus biomineralisierenden Systemen bekannte Prozesse zu vereinfachen und im Experiment nachzustellen. Die gefundenen komplexen hierarchischen Strukturendes Calciumphosphates sind stark von Eigenschaften des Polymerzusatzes abhängig. / The formation of colloidal structures in a time-dependent fashion was followed and analysed for calcium phosphate systems in a watery evironment. A detailed structure analysis was achieved by applying avariety of scattering and imaging methods and comparing the obtained information. The aim of this work was to shed light on processes observed in biomineralizing living systems by simplifying andmimiking those systems in the experiment. A complex hierarchical structuring of calciumphosphate strongly influenced by the added polymer was found.

Techn. University, Diss., 2006--Darmstadt.

Bone turnover has important impacts on bone health. The process modifies weak primary woven bone into the strong lamellar bone, repairs damage in bone, and maintains appropriate calcium homeostasis. The process relies heavily on controlled osteoclastic resorption by dissolution of mineral in the area undergoing remodelling. Bone degenerative diseases occur when the balance between bone resorption and deposition of new bone in the turnover process is altered. Bone is a nanocomposite material composed of a mineral phase (calcium phosphate) deposited within an organic matrix. In spite of the intensive research on the subject, the precise molecular structure of the bone mineral is still an open question. The incorporation of citrate within the mineral structure introduced by Davies et al has provide a more comprehensive structural model that could explain many observations in terms of the mineral structure. Based on this new structural model, a hypothesis has been proposed: that other metabolites similar to citrate can be incorporated into the mineral structure, and differences in metabolite incorporation cause fundamental differences in the physical properties of bone mineral. Thus understanding the effect of metabolite incorporation on the physical properties of bone mineral will lead to insight into the molecular mechanisms of bone degenerative diseases and provide a link between bone quality and bone cell function that is currently missing. Chapter 1 provides overview of the bone composite and formation, and changes in its properties during ageing. The development of the mineral structural model is described and the shortcoming of existing models are assessed. Chapter 2 introduces the theoretical foundations of solid-state NMR spectroscopy, which is the primary analytical method employed in this study, followed by specific experimental techniques that have been used in this work. Chapter 3 described the characterisation of seven different OCP-metabolite composites that have been synthesized in this work, and proposes possible structural model for these composites based on an NMR crystallography approach to determine a structural model for one of the synthetic OCP-metabolite compounds, OCP-SUC. In Chapter 4, the dissolution rate of OCP-metabolites is measured in acidic solution to mimic the resorption process by osteoclasts and assess the possible effects of different incorporated metabolites on the solubility of bone mineral. Finally, Chapter 5 summarises the conclusions from the work and suggests the next steps that arise from this work to uncover the complete molecular structure of bone mineral and its variability in disease.