Sol-gel chemistry of transition metal oxides

This review focuses on calcium phosphate-based bone substitute materials that are used (or can be used) for teeth or bone replacement, bone repair, augmentation, or regeneration. This review will also include some properties of bone (e.g., interconnected porosity, biodegradability, bioactivity, osteoconductivity) that are being mimicked in the manufacture of calcium phosphate-based biomaterials and some of the reported factors and strategies that can make the calcium phosphate-based biomaterials acquire osteoinductive properties. Archaeological findings showed that attempts to replace missing teeth date back to the prehistoric period. The materials used then included shells, corals, ivory (from elephant tusks), metals, and human (from corpses) and animal bones. Because of the practice of cremation in many societies, not much is known about prehistoric materials used to replace bones lost to accident or disease. Presently, autografts (bones obtained from another anatomic site in the same subject) remain the gold standard for bone repair, substitution, and augmentation followed by allografts (bones from another subject, such as processed cadaver bones). Autografts and allografts while having the important advantage of being osteogenic or osteoinductive (i.e., inducing bone formation), suffer from several disadvantages. With autografts the drawbacks include additional expense and trauma to the patient, possibility of donor site morbidity, and limited availability. In the case of allografts, in addition to limited supply and high cost, potential viral transmission and immunogenicity are of serious concern. Because of the high cost and limited availability of autografts and allografts, there is a great need to develop synthetic alternative biomaterials for bone replacement, repair, and augmentation. Current commercial substitute materials to replace or repair teeth and bones include metals, polymers (natural or synthetic), corals, human bones (processed cadaver bones), animal bones (processed cow bones), corals and coral derived, synthetic ceramics (calcium phosphates, calcium sulfates, calcium carbonate, bioactive glasses), and composites. It is interesting to note that several of the materials used in prehistoric times are similar to the materials used presently (e.g., coral and coral derived, animal bone derived, metals). Generally, depending on the ability to stimulate bone tissue, materials for tooth or bone repair or replacement are classified as bioinert or bioactive. Bioinert materials do not stimulate bone formation but instead stimulate formation of fibrous tissue and therefore do not directly bond to bone and thus form a weak biomaterial-bone interface. Bioactive materials stimulate bone tissue formation and therefore directly bond with bone and thus form a uniquely strong biomaterial-bone interface. Bioinert materials include metals (e.g., titanium or titanium alloys, stainless steel, cobalt-chromium, Co-Cr, alloys), some synthetic polymers (e.g., PEEK, Teflon-type), and some ceramics (e.g., alumina, * To whom correspondence should be addressed. Phone: (212) 998-9580. Fax: (212) 995-4244. E-mail: rzl1@nyu.edu. Racquel Zapanta LeGeros received her Ph.D. degree from New York University. She is currently a Professor and Associate Chair of the Department of Biomaterials and Biomimetics at New York University College of Dentistry. Her pioneering work was on substitution in the apatite structure and effect on properties. Her research interests includes biologic and synthetic apatites and related calcium phosphates, calcium phosphatebased biomaterials in the form of granules, scaffolds, cements, and coatings, and implant surface modifications. Her current research is on the development of calcium phosphate-based biomaterial for prevention of bone loss induced by diseases (e.g., osteoporosis), therapy (e.g., radiation), condition (e.g., mineral deficiency, immobility), and recovery of bone loss. She is married to Dr. John P. LeGeros and mother of Bernard, David, Katherine, and Alessandra. Chem. Rev. 2008, 108, 4742–4753 4742

Calcium phosphate-based osteoinductive materials.

Synthesis methods for nanosized hydroxyapatite with diverse structures.

The clinical use of plasma-sprayed hydroxyapatite (HA) coatings on metal implants has aroused as many controversies as interests over the last decade. Although faster and stronger fixation and more bone growth have been revealed, the performance of HA-coated implants has been doubted. This article will initially address the fundamentals of the material selection, design, and processing of the HA coating and show how the coating microstructure and properties can be a good predictor of the expected behavior in the body. Further discussion will clarify the major concerns with the clinical use of HA coatings and introduce a comprehensive review concerning the outcomes experienced with respect to clinical practice over the past 5 years. A reflection on the results indicates that HA coatings can promote earlier and stronger fixation but exhibit a durability that can be related to the coating quality. Specific relationships between coating quality and clinical performance are being established as characterization methods disclose more information about the coating.

Material fundamentals and clinical performance of plasma-sprayed hydroxyapatite coatings: A review

Small, light weight and multifunctional electronic components are attracting much attention because of the rapid growth of the wireless communication systems and microwave products in the consumer electronic market. The component manufacturers are thus forced to search for new advanced integration, packaging and interconnection technologies. One solution is the low temperature cofired ceramic (LTCC) technology enabling fabrication of three-dimensional ceramic modules with low dielectric loss and embedded silver electrodes. During the past 15 years, a large number of new dielectric LTCCs for high frequency applications have been developed. About 1000 papers were published and ∼500 patents were filed in the area of LTCC and related technologies. However, the data of these several very useful materials are scattered. The main purpose of this review is to bring the data and science of these materials together, which will be of immense help to researchers and technologists all over the world. The comme...

Low loss dielectric materials for LTCC applications: a review

Factor group analysis was applied to interpret the vibrational spectra of β-and α-tricalcium phosphate (Ca3(PO4)2). The analysis predicts the number of bands formed due to the splitting of the fundamental vibrational modes of the PO4 3-ion. The number of the infrared and Raman bands predicted by this analysis for the two phases are drastically different and can be ascribed to the difference in atomic arrangements in the two phases resulting in greater shielding of the PO4 3-ions in the β-phase than in the α-phase. Discrepancies in the number of predicted and experimentally-observed bands can be attributed to the weak intensities of some vibrational modes or the convolution of vibrations and limited spectral resolution.

The Infrared and Raman Spectra of β-and α-Tricalcium Phosphate (Ca3(Po4)2)

An FTIR spectral investigation of the structural species found on alumina surfaces

Glass formation limits were determined for the lanthanum borate glasses. Stable immiscibility prevents the formation of clear glasses over the range 0 to 20 mol% La2O3, but excellent quality glasses could be formed between 20 and 28 mol% La2O3. Data are reported for the density, refractive index, thermal expansion coefficient, glass transformation and dilatometric softening temperatures, transformation range viscosity, helium permeability, and chemical durability of these glasses. A limited Raman and infrared spectroscopy study suggests that lanthanum plays a similar structural role in these glasses and in the related crystals.

Properties and Structure of Lanthanum Borate Glasses

Laser-induced Raman spectra were obtained for powders and multidomain single crystals of PbZrO3 at room temperature. Factor-group analysis was used to interpret the spectra on the basis of the space group C2v8-Pba 2. Raman spectra were also observed for single crystals of PbZrO3 at several other temperatures between 76° and 520°K and related to crystal structural changes. No first-order Raman bands were noted above the Curie temperature, indicating a phase transformation to a cubic zirconate structure. The interpretation of Raman spectra for thermally decomposed PbZrO3 is discussed.

Raman Spectrum of PbZrO3

Infrared and Raman spectra were measured and interpreted for two crystalline VPO5 phases (α-and β-VPO5) and several related vanadium phosphate glasses. The spectral results for the crystalline phases were consistent with those predicted by factor group analysis using the previously determined space groups. Empirical band assignments were made for the observed bands on the basis of the bands observed earlier for related phosphate and oxyvanadium compounds. Also, the band assignments made for the infrared spectra of the glasses were consistent with the assignments for crystalline V2O5 and the two crystalline VPO5 phases. No Raman spectra were observed for the glasses because processes involving adsorption and Rayleigh scattering dominated over Raman scattering. The infrared spectra of vanadium phosphate glasses with high P2O5 concentrations possessed many features resembling those observed in the infrared spectra of α-VPO5 suggesting similarities in the short range order for the two materials. Analyses of the vibrational spectra of hydrated α-VPO5 samples suggests that the water molecules are adsorbed in the interlamellar spaces of the crystals, complexing to vanadium ions. Initial steps in the hydration of vanadium phosphate glasses apparently involve physical adsorption of water on their surfaces. No water adsorption could be detected for β-VPO5 under normal conditions from its infrared and Raman spectra.

Robert A. Condrate

Papers

The Infrared and Raman Spectra of β-and α-Tricalcium Phosphate (Ca3(Po4)2)

An FTIR spectral investigation of the structural species found on alumina surfaces

Properties and Structure of Lanthanum Borate Glasses

Raman Spectrum of PbZrO3

The Vibrational Spectra of VPO5 Crystal Phases and Related Glasses