Acellular polyanionic collagen materials intended for biomaterial and tissue engineering uses were prepared by the selective and controlled hydrolysis of carboxyamides from asparagine and glutamine residues of type I collagen present in pericardium, tendon, and intestinal submucosa, all from bovine origin. The increase in carboxyl groups was from 26 +/- 14 (12 h of hydrolysis) to 134 +/- 12 (144 h of hydrolysis). Although collagen triple helix structure of polyanionic materials was preserved in all cases, a decrease in thermal stability and a gradual loss in the ability of collagen molecules to form fibrils were detected with increasing carboxyl content, probably as a result of changes in the pattern of electrostatic interaction. The resulting materials were basically acellular polyanionic collagen matrixes associated with an elastin content dependent on the time of hydrolysis. The results showed that the procedure described in this work may be a useful process for preparation of collagen biomaterials with variable physicochemical properties and macromolecular arrangement with respect to fibril formation and with potential use in tissue engineering.

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Major problems with the treatment of osteomyelitis are associated with poor antibiotic distribution at the site of infection due to limited blood circulation to the skeletal tissue. Improved treatment procedures have been used in drug delivery systems that include bioceramics and natural and synthetic polymers. This work reports the development of anionic collagen:hydroxyapatite composite paste for sustained antibiotic release. Antibiotic release by the composite was characterized by two steps. In the first, 15.0+/-4.9% was released in the first 5 h (n = 53) by a normal Fick diffusion mechanism. In the second step, only 16.8+/-2.2% was released after 7 days. In conclusion, hydroxyapatite:anionic collagen composite can be an efficient support for sustained antibiotic release in the treatment of osteomyelitis because most of the antibiotic release may be associated with composite bioresorption, thus permitting antibiotic release throughout the healing process. Hydroxyapatite:anionic collagen paste showed good biocompatibility associated with bone tissue growth with material still being observed after 60 days from the time of implants.

Recebido em 23/8/96; aceito em 21/5/97 COLLAGEN:CALCIUM PHOSPHATE COMPOSITES. PREPARATION AND CHARACTERIZA-TION. Anionic collagen: calcium phosphate composite was obtained by controlled mixing of collagen and calcium phosphate until the consistence of a past. Material was characterized by a Ca/P ratio of 1.55, with a X-ray diffraction pattern similar to that for hydroxyapatite. Differential Scanning Calorimetry showed that the protein is not denatured under the processing conditions. Scanning Electronic Microscopy showed that the mineral phase are regularly covered with collagen fibers, indicating that anionic collagen is efficient in the preparation of stable form of calcium phosphate ceramic paste.Keywords: composite; collagen; calcium phosphate. ARTIGO INTRODUÇÃOA maioria das biocerâmicas atualmente utilizadas serve apenas como suporte ou matriz para crescimento ósseo. Embora efetivo, esse crescimento é um processo muito lento, fazendo-se necessária a busca de materiais que tornem esse processo mais rápido. Os esforços para obtenção de novas biocerâmicas de fosfato de cálcio têm sido direcionados no sentido de melhorar suas propriedades tanto mecânicas como osteoindutoras, o que pode ser conseguido por meio da associação com polímeros sintéticos 1 , biopolímeros 2 , outras cerâmicas 3 e fatores de indução 4 . A grande aceitação das biocerâmicas à base de sais de fosfato de cálcio deve-se, principalmente, ao seu alto grau de biocompatibilidade, que provavelmente está associado à sua similaridade química com os materiais normalmente encontrados no tecido ósseo. Entre as cerâmicas com melhor desempenho estão os biovidros, alumina, β-tricálcio fosfato e hidroxiapatita (HA) 5 . São utilizadas em ortopedia e traumatologia para correções buco-maxilo-faciais, tumores músculo-esqueléticos, traumatismos raquimedulares e coluna cervical e, em odontologia, nos casos de doenças periodontais, implantes dentários, preenchimento de cavidades císticas e aumentos do rebordo ósseo alveolar 6 . Um dos maiores problemas na utilização da hidroxiapatita na forma particulada é sua dispersão para zonas de tecidos moles, causando problemas como a perda de partículas, redução da zona de correção, desconforto para o paciente, podendo até levar a uma nova cirurgia. A utilização de cerâmicas de fosfato de cálcio na forma de pasta é uma boa alternativa para se evitar tais problemas. De modo particular, o que não ocorre com as biocerâmicas ou qualquer outro material rígido, tais implantes podem ajustar-se perfeitamente aos defeitos, sem haver necessidade de moldagem prévia, já que podem ser moldados e endurecidos in situ, assegurando um melhor ajuste aos tecidos circundantes. A combinação de hidroxiapatita com colágeno 7,8 vem sendo sugerida pois o colágeno constitui-se em agente de união biocompatível e reabsorvível, responsável pela prevenção da migração das partículas cerâmicas até a incorporação pelos tecidos, além de ser um bom suporte para crescimento celular.Este trabalho descreve a preparação e a caracterização de um novo tipo de bi...

Polyanionic collagen obtained from bovine pericardial tissue submitted to alkaline hydrolysis is an acellular matrix with strong potential in tissue engineering. However, increasing the carboxyl content reduces fibril formation and thermal stability compared to the native tissues. In the present work, we propose a chemical protocol based on the association of alkaline hydrolysis with 1,4-dioxane treatment to either attenuate or revert the drastic structural modifications promoted by alkaline treatments. For the characterization of the polyanionic membranes treated with 1,4-dioxane, we found that (1) scanning electron microscopy (SEM) shows a stronger reorientation and aggregation of collagen microfibrils; (2) histological evaluation reveals recovering of the alignment of collagen fibers and reassociation with elastic fibers; (3) differential scanning calorimetry (DSC) shows an increase in thermal stability; and (4) in biocompatibility assays there is a normal attachment, morphology and proliferation associated with high survival of the mouse fibroblast cell line NIH3T3 in reconstituted membranes, which behave as native membranes. Our conclusions reinforce the ability of 1,4-dioxane to enhance the properties of negatively charged polyanionic collagen associated with its potential use as biomaterials for grafting, cationic drug- or cell-delivery systems and for the coating of cardiovascular devices.