磷酸钙骨粘合剂的研究

doi:10.3724/SP.J.1077.2013.12318

摘要/Abstract

摘要：

在柠檬酸中添加壳聚糖配成的固化液与磷酸钙骨水泥(CPC)调和制备的骨修复材料具有类似口香糖的胶状特性, 可应用于碎骨粘结, 称之为磷酸钙骨粘合剂(CPCBA)。本研究考察了柠檬酸的含量对抗压强度、固化时间、水化产物和粘结强度的影响, 同时对该体系进行了初步的体外生物学评价。结果显示, 加入柠檬酸可以缩短固化时间并且时间可以通过柠檬酸的含量进行调控, 同时也改善了抗水性能。壳聚糖可以与骨水泥中的钙离子发生螯合作用, 可以增加界面的粘结强度。小鼠原成骨细胞(MC3T3-E1)在其表面粘附良好, 该体系骨水泥有望取代PMMA成为新的骨粘结剂。

关键词: 磷酸钙, 骨粘结, 骨缺损, 固化

Abstract:

Using citric acid and chitosan as hardening liquid, and calcium phosphate cement (CPC) as powder, gum-like adhesive bone cement is obtained after mixing the powder and liquid components together, which can be used as calcium phosphate cement bone adhesive (CPCBA). The effect of citric acid concentration on compressive strength, setting time and hydration products were investigated. In vitro cytocompatibility of the cements was also researched through cell culture on the cement surface. The results show that setting time is shorten and anti-washout is improved by introducing citric acid. Cohesion strength increases owing to chitosan chelated with calcium ion of CPC. The cements are transformed to hydroxyapatite after incubation 3 d in SBF and osteoblasts (MC3T3-E1) can attach and proliferate on the surface. Results indicate that the calcium phosphate cement bone adhesive is a suitable adhesive material for comminuted fracture.

Key words: calcium phosphate, bone adhesive, bone defect, solidification

中图分类号:

R318

杨盛兵, 王靖, 刘昌胜. 磷酸钙骨粘合剂的研究[J]. 无机材料学报, 2013, 28(1): 85-90.

YANG Sheng-Bing, WANG Jing, LIU Chang-Sheng. Research on Calcium Phosphate Cement Bone Adhesive[J]. Journal of Inorganic Materials, 2013, 28(1): 85-90.

图/表 10

图1 骨块胶粘强度测试示意图

Fig. 1 Schematic illustration of cohesion test

图2 柠檬酸浓度对CPCBA压缩强度的影响

Fig. 2 Effect of citric acid concentration on compressive strength of CPCBA

图3 固化液中柠檬酸含量对抗水性能的影响

Fig. 3 Effect of citric acid concentration on antiwashout

图4 固化液柠檬酸含量对抗水性能的影响

Fig. 4 Effect of citric acid concentration on washout

图5 柠檬酸含量对CPCBA固化时间的影响

Fig. 5 Effect of citric acid concentration on setting time of CPCBA

图6 不同柠檬酸含量CPCBA的XRD分析

Fig. 6 XRD patterns of CPCBA with different citric acid concentration

图7 口香糖状粘性骨水泥

Fig. 7 Gum-like adhesive bone cement

图8 不同柠檬酸含量的CPCBA粘结强度

Fig. 8 Cohesion strength of CPCBA with different citric acid concentration

图9 壳聚糖与钙离子螯合示意图

Fig. 9 Schematic illustration of Ca2+ complex with CS

图10 成骨细胞(MC3T3-E1)接种于含40%柠檬酸骨水泥表面12 h后的表面形貌

Fig . 10 SEM image of osteoblast (MC3T3-E1) cultured for 12 h on the CPCBA surface with 40% citric acid

参考文献 20

[1]	Prevel C D, Eppley B L, Jackson J R, et al. Mini and micro plating of phalangeal and metacarpal fractures: a biomechanical study. J. Hand. Surg. Am., 1995, 20(1): 44-49.
[2]	Gonzalez M H, Hall R F. Intramedullary fixation of metacarpal and proximal phalangeal fracture of the hand. Clin-Orthop, 1996, 327: 47-54.
[3]	Haas S B, Savage R C. Metacarpal fracture fixation with interosseous nylon suture in a patient with metal alleogies. J. Hand. Surg. Am., 1989, 14(1): 107-110.
[4]	Gorosh J, Page B J. Treatment of phalangeal fractures of the hand with introosscons wire fixation. Orthop. Rev., 1989, 18(7): 800-806.
[5]	Zhou Y J, Liu S C, Li X, et al. Surgical treatment of comminuted fracture near joints. Jounal of Practicle Orthoedics, 2001, 7(4): 291-292.
[6]	Spicer P P, Mikos A G. Fibrin glue as a drug delivery system. J. Controlled Release, 2010, 148(1):49-55.
[7]	Bauer N B, Brinke N, Heiss C, et al. Biodegradable beta-Tri-calciumphosphate/hydroxyethyl methacrylate enhanced three component bone adhesive demonstrates biocompatibility without evidence of systemic toxicity in a rabbit model. J. Biomed. Mater. Res. B Appl. Biomater., 2009, 90B(2): 767-777.
[8]	Nihouannen D L, Saffarzadeh A, Gauthier O, et al. Bone tissue formation in sheep muscles induced by a biphasic calcium phosphate ceramic and fibrin glue composite. J. Mater. Sci: Mater. Med., 2008, 19(2): 667-675.
[9]	刘昌胜. 新型骨修复材料-磷酸钙骨水泥的制备及其应用基础研究. 上海: 华东理工学博士论文, 1996.
[10]	Zhu M G. New technics preparation of HAp bone cement material with Sol-Gel method. Metallic Functional Materials, 2002, 9(1): 33-35.
[11]	Buranapanitkit B, Srinilta V, Ingviga N, et al. The efficacy of a hydroxyapatite composite as a biodegradable antibiotic delivery system. Clinical Orthopaedics and Related Research, 2004, 424: 244-252.
[12]	Xu H K, Simon C G. Fast setting calcium phosphate-chitosan scaffold: mechanical properties and biocompatibility. Biomaterials, 2005, 26(12): 1337-1348.
[13]	Brown W E, Chow L C. A new calcium phosphate water-setting cement. Cem. Res. Prog., 1986, 4: 352-379.
[14]	Kokubo T, It O S, Huang I, et al. CaO-SiO2-P2O5 as a bioactive bone cement. J. Am. Ceram Soc., 1991, 74: 1739-1741.
[15]	Barralet J E, Hofmann M, Grover L M, et al. High-strength apatitic cement by modification with α-hydroxy acid salts. Advanced Materials, 2003, 15(24): 2091-2094.
[16]	Yokoyama A, Yamamoto S, Kawasaki T, et al. Development of calcium phosphate cement using chitosan and citric acid for bone substitute materials. Biomaterials, 2002, 23(4): 1091-1101.
[17]	Liu H, Li H, Cheng W J, et al. Novel injectable calcium phosphate/ chitosan composites for bone substitute materials. Acta Biomaterialia, 2006, 2(5): 557-565.
[18]	Xu H K, Simon C G. Fast seting calcium phosphate chitosan scaffold: mechanical properties and biocompatibility. Biomaterials, 2005, 26(12): 1337-1348
[19]	Gbureck U, Barralet J E, Spatz K, et al. Ionic modification of calcium phosphate cementviscosity. Part1: hypodermic injection and strength improvement of apatite cement. Biomaterials, 2004, 11: 2187-2195.
[20]	Webster A, Halling M D, Grant D M. Metal complexation of chitosan and its glutaraldehyde cross-linked derivative. Carbohydrate Research, 2007, 342: 1189-1201.