The mineralized tissue of intertubular dentin is a collagen-mineral composite with considerable local variations of mechanical properties. Area scans of human coronal dentin were made by complementary methods to investigate correlations between local mechanical properties and the density, size, and crystallinity of the mineral particles. Scanning images from the same specimen were collected with Fourier-transform infrared microspectroscopy in reflectance mode (FTIR-RM), small angle X-ray scattering (SAXS), quantitative backscattered electron imaging (qBEI), and Nanoindentation in an atomic force microscope. The mineral content of dentin was found to decrease and the thickness of mineral crystals to increase towards the dentin-enamel junction (DEJ). Hardness and elastic modulus both decreased towards the DEJ. In a correlation analysis, the mineral content and, even more, the thickness of mineral crystals were found as the best predictors of hardness. The dentin layer close to the DEJ corresponds to a local minimum in hardness and elastic modulus, a configuration known to be an effective obstacle for crack propagation. Hence, the observed variations of mechanical and structural properties in an area between 0 and 1.5 mm below the DEJ define crown dentin as a gradient material optimized for its mechanical function.

Well‐dispersed multiwalled carbon nanotube (MWNT)/polystyrene nanocomposites have been prepared via melt extrusion, using trialkylimidazolium tetrafluoroborate‐compatibilized MWNTs. Quantification of the improvement is realized via transmission electron microscopy and laser scanning confocal microscopy image analysis. Differential scanning calorimetry and Fourier‐transform infrared and X‐ray diffraction analysis show evidence for a π‐cation, nanotube–imidazolium interaction and the conversion from an interdigitated bilayer, for the imidazolium salt, to an ordered lamellar structure, for the imidazolium on the surface of the MWNTs.

W hat are biominerals and how are they formed? It is usually assumed: (i) that the prototype for most apatitic biominerals is hydroxyapatite (OHAp), Ca 5 (PO 4 ) 3 OH; and (ii) that the OHAp structure has been modified by the presence of impurity ions and vacancy defects in specific OHAp lattice sites. The usual answer, at least implicitly, to the second question is that the apatitic mineral is formed directly by the precipitation of ions from the surrounding solution. Our answers are: (i) that apatitic biominerals are formed through a precursor mechanism in which octacalcium phosphate (OCP), Ca 8 H 2 (PO4) 6 -5H 2 O, precipitates first and then hydrolyzes irreversibly in situ to a transition product intermediate to OCP and OHAp; and (ii) that this product, "octacalcium phosphate hydrolyzate" (OCPH), may contain (a) OHAp-like and OCP-like domains in varying amounts, (b) vacancy defects and impurity ions in lattice sites in these domains, and (c) various kinds of one-, two-, and threedimensional defects which are not present in either the OHAp or the OCP lattice, these defects being formed during the in situ hydrolysis step.A calcification model of this type was first proposed in 1957, but full acceptance was delayed because most of the evidence was circumstantial and in vitro in nature. The situation has changed radically because of three unrelated studies that are in vivo in nature but lead to the same conclusion:I. 32 P-pyrolysis studies of rat enamel: The results clearly demonstrated that an acidic calcium phosphate precursor was involved.II. Precipitation of calcium phosphates in serum. Ultrafiltered serum was equilibrated with brushite. Subsequent changes in the ionic concentrations revealed that OCP was formed at first and then hydrolyzed to a more basic form, OCPH, but never reached the solubility of OHAp.HI. Physicochemical properties of cardiovascular biominerals: We recently characterized biominerals in cardiovascular deposits in an encompassing variety of ways. As an overall conclusion, OCPH was the prototype most compatible with the data [including indices of refraction, solubility, P 2 O 7 4~ formation on pyrolysis, thermogravimetric analysis (TGA) measurements, presence of water, and incorporation of CO 3 2 ", Na + , and Mg 2+ ]. This calcification model has important consequences relative to all kinds of calcification and decalcification processes, including those of enamel.

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We investigated a novel polyepoxide crosslinker that was hypothesized to confer both material stabilization and calcification resistance when used to prepare bioprosthetic heart valves. Triglycidylamine (TGA) was synthesized via reacting epichlorhydrin and NH(3). TGA was used to crosslink porcine aortic cusps, bovine pericardium, and type I collagen. Control materials were crosslinked with glutaraldehyde (Glut). TGA-pretreated materials had shrink temperatures comparable to Glut fixation. However, TGA crosslinking conferred significantly greater collagenase resistance than Glut pretreatment, and significantly improved biomechanical compliance. Sheep aortic valve interstitial cells grown on TGA-pretreated collagen did not calcify, whereas sheep aortic valve interstitial cells grown on control substrates calcified extensively. Rat subdermal implants (porcine aortic cusps/bovine pericardium) pretreated with TGA demonstrated significantly less calcification than Glut pretreated implants. Investigations of extracellular matrix proteins associated with calcification, matrix metalloproteinases (MMPs) 2 and 9, tenascin-C, and osteopontin, revealed that MMP-9 and tenascin-C demonstrated reduced expression both in vitro and in vivo with TGA crosslinking compared to controls, whereas osteopontin and MMP-2 expression were not affected. TGA pretreatment of heterograft biomaterials results in improved stability compared to Glut, confers biomechanical properties superior to Glut crosslinking, and demonstrates significant calcification resistance.

Objectives The objectives of this study were to 1) demonstrate X-ray microcomputed tomography (μCT) as a viable method for determining the polymerization shrinkage and microleakage on the same sample accurately and non-destructively, and 2) investigate the effect of sample geometry (e.g., C-factor and volume) on polymerization shrinkage and microleakage. Methods Composites placed in a series of model cavities of controlled C-factors and volumes were imaged using μCT to determine their precise location and volume before and after photopolymerization. Shrinkage was calculated by comparing the volume of composites before and after polymerization and leakage was predicted based on gap formation between composites and cavity walls as a function of position. Dye penetration experiments were used to validate μCT results. Results The degree of conversion (DC) of composites measured using FTIR in reflectance mode was nearly identical for composites filled in all model cavity geometries. The shrinkage of composites calculated based on μCT results was statically identical regardless of sample geometry. Microleakage, on the other hand, was highly dependent on the C-factor as well as the composite volume, with higher C-factors and larger volumes leading to a greater probability of microleakage. Spatial distribution of microleakage determined by μCT agreed well with results determined by dye penetration. Significance μ CT has proven to be a powerful technique in quantifying polymerization shrinkage and corresponding microleakage for clinically relevant cavity geometries.