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Polyurethanes based on poly(epsilon-caprolactone) (PCL) (750-2800 g/mol) and 1,4-butane diisocyanate (BDI) with different soft segment lengths and constant uniform hard segment length were synthesized in absence of catalysts for the production of a degradable meniscus scaffold. First the polyesterdiols were endcapped with BDI yielding a macrodiisocyanate with a minimal amount of side reactions and a functionality of 2.0. Subsequently, the macrodiisocyanates were extended with 1,4-butanediol in order to obtain the corresponding polyurethane. The polyurethanes had molecular weights between 78 and 160 kg/mol. Above molar masses of 1900 g/mol of the polyesterdiol crystalline PCL was found while the hard segment showed an increase in melting point from 78 to 122 degrees C with increasing hard segment content. It was estimated that the percentage crystallinity of the hard segment varied between 92 and 26%. The Young's modulus varied between 30 and 264 MPa, the strain at break varied between 870 and 1200% and tear strengths varied between 97 and 237 kJ/m2.

The porous polymer implant developed into a polymer-tissue construct that resembled the native meniscus, and with improved gliding characteristics, this prosthesis might be a promising implant for the replacement of the meniscus.

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Please be advised that this information was generated on 2018-05-12 and may be subject to change.ELSEVIER lìiom atorìals 17 ( 1 Otiti) H ì U -m © lí)í)(¡ lílsHvior Scioncci lim itiu l I'rintod in Groat Britain, A ll rights msorvod 0t42-i)(il2/5)(>/$15.00 R . P . H . V e t h t a n d H . W . B . J a n s e n 1 In the past, porous materials made of an aromatic polyurethane (PU) were successfully used for meniscal reconstruction in dogs. Since aromatic PUs yield very toxic fragments upon degradation, a linear PU was synthesized by curing a poly(i-caprolactone) and 1,4-frans-cyclohexane diisocyanate based prepolymer with cyclohexanedimethanol. Porous materials of this polymer were also implanted for meniscal reconstruction. The results were comparable with the most successful implant series so far. Additionally, a porous meniscal prosthesis was developed to replace a total meniscus. Due to the very high shear stresses to which the prosthesis would be exposed, the stress hysteresis phenom enon linear PUs are known to exhibit could be of great consequence. Therefore an aliphatic PU network, synthesized by cross-linking poly(f:-caprolactone) and 1,4-frans-cyclohexane diisocyanate with glycerol, was used. Dislocation caused by tearing out of the sutures was found to be a problem because the tear resistance of the material was relatively low. In this study the tearing problem has been partly circumvented by using a complex suturing technique. Meniscal prostheses turned out to induce fibrocartilage upon implantation, and degeneration of articular cartilage was less severe than after meniscectomy.

In earlier studies, meniscal replacement with a porous polymer implant led to regeneration of neo-meniscal tissue. To evaluate the influence of the chemical properties on the tissue regeneration in the implant, in the present study, the meniscus in the dog's knee was replaced with either an aromatic 4,4-diphenylmethanediisocyanate based polyesterurethane implant (Estane) (n = 6) or with an aliphatic 1,4-butanediisocyanate based polyesterurethane implant (PCLPU) (n = 6). After 6 months, the knee joints were resected and the tissue behavior in the two different prostheses was evaluated microscopically. In both prostheses, a meniscus-like distribution of the tissue phenotype was found with collagen type I in the peripheral fibrous zones and collagen type II in the central, more cartilaginous zones. The compression-stress behavior of the implant-tissue construct remained in between the stiffness of the polymer material and that of the native meniscus. The PCLPU implant seemed to provoke less synovial tissue reaction. After meniscectomy solely, in 5 out of 6 cases, a meniscus-like regenerate was formed. Furthermore, the articular cartilage degeneration after placing a PCLPU implant did also not exceed the degeneration after the Estane implant or after meniscectomy. The differences between these two implants did not seem to influence the tissue regeneration in the implant. However, PCLPU seemed to evoke less tissue reaction and, therefore, is thought to be less or even nontoxic as compared with the Estane implant. Therefore, for studies in the future, the authors prefer the PCLPU prostheses for replacement of the meniscus.

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