生物可吸收高强度固态压缩聚丙交酯的降解特征和强度维持

用特殊的加热压缩方法固态压缩法 (solid statecompression ,SC)加工左旋聚丙交酯 (poly L lac tide ,PLLA) ,获得高强度SC PLLA(弯曲强度 2 5 0Mpa,剪切强度 190Mpa)。将SC PLLA棒 (3.2mm× 30mm) ,置于PBS液或植入兔的皮下和股骨内 ,定期观察粘均分子量、结晶度、扫描电镜 (SEM )形态和机械性能 (弯曲强度和剪切强度 ) ,研究该材料的降解特征和强度特性 ,以评价其作为矫形外科骨固定装置材料的价值。结果表明 ,各组分子量在前 12周下降迅速 ,其后缓慢下降 ,至 72周时 ,各组分子量降解 98%以上 ;结晶度则与此相反 ,12周内上升迅速 ,36周达最大。SEM见SC PLLA降解前内部有大量排列整齐的纵向纤维 ,并随降解而破坏并出现孔隙。SC PLLA降解 2 4周后 ,各组的弯曲强度仍维持在 180MPa以上 ,剪切强度在 75MPa以上 ,都大于皮质骨强度 ,提示材料的强度维持时间满足一般的骨内固定要求。因此SC PLLA是一种有前途的生物可吸收接骨材料     

聚L乳酸/β-磷酸三钙可吸收材料体内降解过程中的生物力学特性

背景：临床应用的金属内固定材料初始弯曲强度及弹性模量约为皮质骨的4倍及20倍,其力学性能不能随骨愈合过程动态变化,出现医学上的“应力遮挡效应”,影响骨愈合且需要二次手术取出。 目的：观察β-磷酸三钙与聚L乳酸复合可吸收内固定材料在动物体内降解后的生物力学特性。 方法：在30只新西兰大白兔腰背部左侧皮下植入聚L乳酸可吸收棒状材料为对照组,右侧植入聚L乳酸/β-磷酸三钙可吸收棒状材料作为实验组。于术前及术后4,8,12,16,24周观察两组材料的弯曲强度、剪切强度及扭转强度。 结果与结论：降解过程中两组材料的弯曲强度、剪切强度及扭转强度随时间的延长呈逐步下降趋势;术后12,16,24周实验组材料弯曲强度均高于对照组材料(P < 0.05)。术后4,8,12,16,24周实验组材料剪切强度均高于对照组材料(P < 0.05)。术后各时间点实验组材料扭转强度均稍高于对照组材料,但差异无显著性意义(P > 0.05)。说明聚L乳酸/β-磷酸三钙可吸收材料的体内降解速度较纯聚L乳酸慢,其力学强度能维持较长时间,可满足松质骨骨折的固定及骨组织愈合的要求。     

聚左旋丙交酯骨折内固定物体外降解研究

通过左旋丙交酯开环聚合法制取分子量42万的聚左旋丙交酯（PLLA）用于制备可降解骨折内固定物。由PLLA原料经不同的成型工艺方法制备了三种棒状骨折棒状骨折内固定物试样。A试样：将PLLA块状原料直接切削加工成棒状物；B试样：将A试样由乙酸乙酯进行抽提；C试样：将PLLA块状原料粉碎抽提后进行熔融挤出和热拉伸。三种试样在37℃生理盐缓冲液中降解280天。考察了试样的分子量、弯曲性能、重点及缓冲液中乳酸浓度等随时间的变化规律。结果表明：不同的成型工艺，PLLA骨折内固定物的降解有很大差异，C试样的加工成型方法最为理想。因此我们认为：用PLLA材料选定合理的成型工艺方法可以制取满足临床应用要求的骨折内固定物。     

ε-己内酯与DL-丙交酯共聚物的体内降解性能

背景：ε-己内酯与DL-丙交酯共聚后具有良好的生物相容性和可调控的降解速率,它的应用与其体内降解性能有着重要关系。 目的：观察聚(己内酯-co-DL-丙交酯)在大耳白兔体内的降解性能。 方法：将不同配比DL-丙交酯和ε-己内酯组成的聚(己内酯-co-DL-丙交酯)制备成不同尺寸的试样,植入到日本大耳白兔背部皮下,定期观察试样的形态、失重率、相对分子质量和热性能。 结果与结论：随着ε-己内酯投料比的增加,聚(己内酯-co-DL-丙交酯)形状保持能力增强,降解速度减慢;相同共聚组成的试样,尺寸越大,降解速度越快。     

聚DL-丙交酯/羟基磷灰石(PDLLA/HA)复合材料(I):制备及力学性能

将羟基磷灰石(HA)与DL-丙交酯(DL-LA)按一定比例混合,在辛酸亚锡引发下开环聚合得到HA微粒填充的聚DL-丙交酯/羟基磷灰石(PDLLA/HA)复合材料.在一定引发剂浓度下,HA的含量越大,粒径越小,PDLLA的分子量越低.扫描电子显微镜观察HA微粒均匀分布在PDLLA基质中,当PDLLA的分子量在175000～245000范围内,HA含量(HAwt%)为30%时,复合材料的弯曲强度达90MPa,剪切强度为72MPa,模量为6.9GPa,均高于其它体系.HA的引入不仅提高了材料的初始力学强度,而且还延缓了PDLLA的降解速度.     

聚-L-乳酸/β-磷酸三钙复合物生物可吸收骨折内固定棒的体内降解和组织相容性

将β-磷酸三钙(β-TCP)与聚-L-乳酸(PLLA)复合得到PLLA/β-TCP复合材料,用注射成型方法制备出可吸收骨折内固定棒,然后通过分子量、质量变化、扫描电镜观察、弯曲强度变化和组织学方法等研究可吸收骨折内固定棒的体内降解过程。结果表明,降解初期聚乳酸的分子量有大幅度下降,重量损失滞后。随着降解的进行,可吸收棒表面逐渐粗糙,内部逐渐出现微孔和小“沟壑”,弯曲强度从初始的151MPa下降至12周的106MPa。组织学分析显示,PLLA/β-TCP复合材料具有良好的组织相容性。     

左旋聚乳酸可吸收骨钉两种灭菌法效果评价

目的评价左旋聚乳酸可吸收骨钉经环氧乙烷灭菌和^60Co-γ辐照灭菌的效果。方法将左旋聚乳酸可吸收骨钉放人环氧乙烷灭菌器中灭菌,灭菌后将材料置于空气中静置5d,以清除残留的环氧乙烷;另将左旋聚乳酸可吸收骨钉采用^60Co-γ辐照灭菌装置灭菌,吸收剂量15kGy。然后对2种方法灭菌的骨钉分别进行性能表征。结果与左旋聚乳酸可吸收骨钉初始弯曲强度相比,经2种方法灭菌的骨钉弯曲强度均无明显下降（P〉0．05）;与左旋聚乳酸可吸收骨钉初始分子量相比,经^60Co-γ辐照灭菌的骨钉分子量明显减小,下降约11％,表明材料发生降解;经环氧乙烷灭菌的骨钉分子量无明显变化,下降约3％,表明材料未发生明显降解。结论左旋聚乳酸可吸收骨钉以环氧乙烷灭菌为佳。     

定向拉伸工艺对可吸收肩袖补片力学性能的影响

目的研究定向拉伸工艺对不同可吸收补片力学性能的影响,评价其作为肩袖损伤修复补片的潜力。方法采用定向拉伸工艺制备聚乳酸基材料的可吸收补片,设定不同的定向拉伸温度(50～80℃)和拉伸比(0. 5～4. 3),研究不同参数对不同材料可吸收补片力学性能的影响,同时对其热性能、结晶性能和表面形貌进行表征。结果定向拉伸温度和拉伸比可以调控可吸收补片的拉伸强度和拉伸应变、热性能、结晶性能和微观形貌。当拉伸温度分别为60、70、70℃,对应的拉伸比分别为3、3、4. 3时,聚-L-丙交酯-乙交酯的共聚物(PLGA)、聚-L-丙交酯-D,L-丙交酯的共聚物(PLDLLA)、聚-L-丙交酯-ε-己内酯的共聚物(PLC)最大拉伸强度分别为(74±7)、(97±6)、(107±8) MPa,大于犬类冈下肌腱的力学强度(40 MPa),但仅有PLDLLA补片的应变满足天然肩袖的柔韧性。结论定向拉伸工艺可以提高可吸收补片的力学性能,PLDLLA补片具有增强肩袖撕裂的潜力。     

3D打印PLCL/PLLA复合材料支架的体外降解性能研究

目的 探讨左旋聚乳酸(PLLA)与聚-L-丙交酯-己内酯(PLCL)的复合对PLCL的三维(3D)打印性能及其打印支架降解性能的影响.方法 采用共混手段制备了系列不同比例的PLCL(100％、90％、80％、70％、60％、50％)为基质相、PLLA(10％、20％、30％、40％、50％、100％)为分散相的复合材料...     

聚DL-丙交酯/羟基磷灰石(PDLLA/HA)复合材料(I):制备及力学性能

将羟基磷灰石 (HA)与DL 丙交酯 (DL LA)按一定比例混合 ,在辛酸亚锡引发下开环聚合得到HA微粒填充的聚DL 丙交酯 /羟基磷灰石 (PDLLA/HA)复合材料。在一定引发剂浓度下 ,HA的含量越大 ,粒径越小 ,PDLLA的分子量越低。扫描电子显微镜观察HA微粒均匀分布在PDLLA基质中 ,当PDLLA的分子量在 175 0 0 0～ 2 45 0 0 0范围内 ,HA含量 (HAwt %)为 30 %时 ,复合材料的弯曲强度达 90MPa ,剪切强度为 72MPa,模量为 6 .9GPa ,均高于其它体系。HA的引入不仅提高了材料的初始力学强度 ,而且还延缓了PDLLA的降解速度。     

In vitro and in vivo studies on bioabsorbable ultra-high-strength poly(L-lactide) rods.

Ultra-high-strength poly(L-lactide) (PLLA) rods were fabricated using a drawing technique. Rods with a diameter of 3.2 mm and a draw ratio of 2.5:1 showed initial bending strength and modulus values of 240 MPa and 13 GPa, respectively. The purpose of this study was to investigate the in vitro and in vivo degradation of PLLA rods with a draw ratio of 2.5:1. The greater the rod diameter, the longer the bending strength was maintained in phosphate buffered saline at 37 degrees C. The bending strength retention of rods (diam. 3.2 mm) implanted in the subcutis of rabbits was almost equal to that of rods in the in vitro study, while those rods implanted in the medullary cavity of rabbit femora showed a slightly lower bending strength retention. Molecular weight was reduced to the greatest extent in the medullary cavity, followed by in the subcutis and in vitro. The weight of PLLA rods in the medullary cavity was reduced by 22% at 52 weeks and by 70% at 78 weeks after implantation. Histologically, no inflammatory or foreign body reaction was observed in the medullary cavity for 52 weeks. The drawn PLLA rods maintained a bending strength exceeding that of human cortical bone in the medullary canal for a period of 8 weeks, suggesting that the drawn PLLA rods may be useful in the repair of fractured human bones.     

Fixation of distal femoral osteotomies with self-reinforced poly(L/DL)lactide 70 : 30 and self-reinforced poly(L/DL)lactide 70 : 30/bioactive glass composite rods. An experimental study on rabbits

Two self-reinforced poly(L/DL)lactide 70 : 30 or self-reinforced poly(L/DL)lactide 70 : 30/bioactive glass (SR-P(L/DL)LA/bioactive glass) composite rods (2 mm × 40 mm) were implanted into the dorsal subcutaneous tissue and osteotomies of the distal femur were fixed with these rods (2 mm × 26 mm) in 36 rabbits. The follow-up times varied from 3 to 100 weeks. After the animals were killed, three-point bending and shear tests and molecular weight measurements were performed for subcutaneously placed rods. Radiological, histological, histomorphometrical, microradiographic and oxytetracycline-fluorescence studies of the osteotomized and intact control femora were performed. After 12 weeks the SR-P(L/DL)LA rods had fragmented into pieces and the mechanical properties could not be measured. The SR-P(L/DL)LA/bioactive glass rods lost their mechanical properties slower, and at 24 weeks the bending strength had decreased by 39% and the shear strength by 50%. After that the mechanical properties of the SR-P(L/DL)LA/bioactive glass rods could not be measured. All osteotomies healed well, and no gross signs of inflammatory reactions were observed. One slight displacement was seen in the three-week follow-up group with SR-P(L/DL)LA rods. Signs of resorption of the implants were seen after 48 weeks in the SR-P(L/DL)LA group and after 24 weeks in the SR-P(L/DL)LA/bioactive glass group. The SR-P(L/DL)LA/bioactive glass rods were almost totally resorbed from the bone at 100 weeks. The present investigation showed that the mechanical strength and fixation properties of the SR-P(L/DL)LA and the SR-P(L/DL)LA/bioactive glass composite rods are suitable for fixation of cancellous bone osteotomies in rabbits.     

Self-reinforced composites of bioabsorbable polymer and bioactive glass with different bioactive glass contents. Part I: Initial mechanical properties and bioactivity

Spherical bioactive glass 13-93 particles, with a particle size distribution of 50-125 microm, were combined with bioabsorbable poly-L,DL-lactide 70/30 using twin-screw extrusion. The composite rods containing 0, 20, 30, 40 and 50 wt% of bioactive glass were further self-reinforced by drawing to a diameter of approximately 3 mm. The bioactive glass spheres were well dispersed and the open pores were formed on the composite surface during drawing. The initial mechanical properties were studied. The addition of bioactive glass reduced the bending strength, bending modulus, shear strength, compression strength and torsion strength of poly-L,DL-lactide. However, the strain at maximum bending load increased in self-reinforced composites. Initially brittle composites became ductile in self-reinforcing. The bioactivity was studied in phosphate buffered saline for up to 12 days. The formation of calcium phosphate precipitation was followed using scanning electron microscopy and energy dispersive X-ray analysis. Results showed that the bioactive glass addition affected the initial mechanical properties and bioactivity of the composites. It was concluded that the optimal bioactive glass content depends on the applications of the composites.     

Fixation of distal femoral osteotomies with self-reinforced poly(L/DL)lactide 70:30 and self-reinforced poly(L/DL)lactide 70: 30/bioactive glass composite rods. an experimental study on rabbits

Two self-reinforced poly(L/DL)lactide 70:30 or self-reinforced poly (L/DL)lactide 70:30/ bioactive glass (SR-P(L/DL)LA/bioactive glass) composite rods (2 mm x 40 mm) were implanted into the dorsal subcutaneous tissue and osteotomies of the distal femur were fixed with these rods (2 mm x 26 mm) in 36 rabbits. The follow-up times varied from 3 to 100 weeks. After the animals were killed, three-point bending and shear tests and molecular weight measurements were performed for subcutaneously placed rods. Radiological, histological, histomorphometrical, microradiographic and oxytetracycline-fluorescence studies of the osteotomized and intact control femora were performed. After 12 weeks the SR-P(L/DL)LA rods had fragmented into pieces and the mechanical properties could not be measured. The SR-P(L/DL)LA/bioactive glass rods lost their mechanical properties slower, and at 24 weeks the bending strength had decreased by 39% and the shear strength by 50%. After that the mechanical properties of the SR-P(L/DL)LA/bioactive glass rods could not be measured. All osteotomies healed well, and no gross signs of inflammatory reactions were observed. One slight displacement was seen in the three-week follow-up group with SR-P(L/DL)LA rods. Signs of resorption of the implants were seen after 48 weeks in the SR-P(L/DL)LA group and after 24 weeks in the SR-P(L/DL)LA/bioactive glass group. The SR-P(L/DL)LA/bioactive glass rods were almost totally resorbed from the bone at 100 weeks. The present investigation showed that the mechanical strength and fixation properties of the SR-P(L/DL)LA and the SR-P(L/DL)LA/bioactive glass composite rods are suitable for fixation of cancellous bone osteotomies in rabbits.     

Prostaglandin E1 and recombinant bone morphogenetic protein effect on strength of hydroxyapatite implants.

Although combinations of hydroxyapatite (HAP) and bone morphogenetic protein (BMP) are expected to provide potent alternatives to autogenous bone grafts, it is still anticipated that substances that act synergistically with BMP will be found because the inducing potential of purified BMP in bone is not strong enough. We already have shown that prostaglandin (PG) E1 has a strong and dose-dependent synergistic effect on the osteoinductive activity induced by recombinant human (rh) BMP and that it enhances osteoconduction even when used alone. In this study, porous HAP rods were treated as follows: (1) without PGE1 or rhBMP (control group); (2) with varying concentrations of PGE1; and (3) with varying concentrations of PGE1 combined with 1 microg of rhBMP-2. The rods were subperiosteally implanted on the cranial bone of rabbits to evaluate the effect of these treatments on the mechanical strength of the implanted HAP rods. The HAP rods were removed 3, 6, or 9 weeks after implantation and subjected to mechanical strength determinations. The control group (no addition of BMP to the rods) showed no significant increase in three-point bending strength or in compression strength compared to pre-implantation. On the other hand, PGE1 combined with rhBMP had a strong and dose-dependent effect on the mechanical strength of HAP, increasing it significantly, especially compression strength. PGE1 also increased mechanical strength even when used alone. Histological examination revealed that PGE1, whether or not it was combined with rhBMP, increased bone formation into the pores of HAP and consequently increased the mechanical strength of porous HAP.     

Loss of mechanical properties in vivo and bone–implant interface strength of AZ31B magnesium alloy screws with Si-containing coating

In this study the loss of mechanical properties and the interface strength of coated AZ31B magnesium alloy (a magnesium–aluminum alloy) screws with surrounding host tissues were investigated and compared with non-coated AZ31B, degradable polymer and biostable titanium alloy screws in a rabbit animal model after 1, 4, 12 and 21 weeks of implantation. The interface strength was evaluated in terms of the extraction torque required to back out the screws. The loss of mechanical properties over time was indicated by one-point bending load loss of the screws after these were extracted at different times. AZ31B samples with a silicon-containing coating had a decreased degradation rate and improved biological properties. The extraction torque of Ti6Al4V, poly-l-lactide (PLLA) and coated AZ31B increased significantly from 1 week to 4 weeks post-implantation, indicating a rapid osteosynthesis process over 3 weeks. The extraction torque of coated AZ31B increased with implantation time, and was higher than that of PLLA after 4 weeks of implantation, equalling that of Ti6Al4V at 12 weeks and was higher at 21 weeks. The bending loads of non-coated AZ31B and PLLA screws degraded sharply after implantation, and that of coated AZ31B degraded more slowly. The biodegradation mechanism, the coating to control the degradation rate and the bioactivity of magnesium alloys influencing the mechanical properties loss over time and bone–implant interface strength are discussed in this study and it is concluded that a suitable degradation rate will result in an improvement in the mechanical performance of magnesium alloys, making them more suitable for clinical application.     

Tensile properties and biological response of poly(L-lactic acid) felt graft: an experimental trial for rotator-cuff reconstruction

Poly(L-lactic acid) felt (PLLA felt) was prepared for reconstruction of the rotator cuff in animal models. Small changes were found in the tensile strength of both the cultured PLLA felt and the PLLA felt implanted on the paravertebral muscle of rabbits up to 16 postoperative weeks. The stiffness of the felt implanted on the muscle from 6 to 16 weeks showed a statistically significant increase. When the infraspinatus tendons of beagle dog were reconstructed with the PLLA felt, the ultimate strength of PLLA felt increased threefold, and the stiffness increased fivefold by 16 postoperative weeks compared to that of the initial PLLA felt. They were statistically significant (p < 0.01). All the implanted specimens ruptured at the junction between the bone and the PLLA felt. Histological examination demonstrated infiltration of fibrous tissue into the interstices of the PLLA felt fibers. Connection between the infraspinatus tendon and the PLLA felt was tight with the formed scar tissue, but the connective tissue between the bone and PLLA felt fibers was sparse even at 16 and 32 postoperative weeks. A few deteriorated PLLA felt fibers were observed at 32 postoperative weeks. It was concluded that the degradation rate of PLLA felt was low and the tensile recovery of the PLLA felt graft in beagle dogs was excellent. Thus, PLLA felt might be a useful bioabsorbable material for rotator-cuff reconstruction.     

Processing, annealing and sterilisation of poly-L-lactide

Poly-L-lactide (PLLA) is one of the most significant members of a group of polymers regarded as bioabsorbable. Degradation of PLLA proceeds through hydrolysis of the ester bonds in the polymer chains and is influenced significantly by the polymer's molecular weight and crystallinity. To evaluate the effects of processing and sterilisation on these properties, PLLA pellets were either compression moulded or extruded, subjected to annealing at 120 degrees C for 4h and sterilised by ethylene oxide (EtO) gas. Procedures were used to evaluate the mechanical properties, molecular weight and crystallinity. Upon processing, the crystallinity of the material fell from 61% for the PLLA pellets to 12% and 20% for the compressed and extruded components, respectively. After annealing, crystallinity increased to 43% for the compression-moulded material and 40% for the extruded material. Crystallinity further increased upon EtO sterilisation. A slight decrease in molecular weight was observed for the extruded material through processing, annealing and sterilisation. Young's modulus generally increased with increasing crystallinity, and extension at break and tensile strength decreased. The results from this investigation suggest that PLLA is sensitive to processing and sterilisation, altering properties critical to its degradation rate.     

Nano-composite of poly(L-lactide) and surface grafted hydroxyapatite: mechanical properties and biocompatibility

In order to improve the bonding between hydroxyapatite (HAP) particles and poly(L-lactide) (PLLA), and hence to increase mechanical properties of the PLLA/HAP composite as potential bone substitute material, the HAP nano-particles were surface-grafted with PLLA and further blended with PLLA. The structure and properties of the composites were subsequently investigated by the mechanical property testing, the differential scanning calorimeter measurements (DSC), the scanning electron microscopy (SEM), the polarized optical microscopy (POM), and the cell culture. The PLLA molecules grafted on the HAP surfaces, as inter-tying molecules, played an important role in improving the adhesive strength between the particles and the polymer matrix. At a low content (approximately 4 wt%) of surface grafted-HAP (g-HAP), the PLLA/g-HAP nano-composites exhibited higher bending strength and impact energy than the pristine PLLA, and at a higher g-HAP content (e.g., 20 wt%), the modulus was remarkably increased. It implied that PLLA could be strengthened as well as toughened by g-HAP nano-particles. The results of biocompatibility test showed that the g-HAP existing in the PLLA composite facilitated both adhesion and proliferation of chondrocytes on the PLLA/g-HAP composite film.