Research on Biological Bone Adhesion Properties of Polyurethane Composite with Disulfide Bond in Hard Segment
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摘要: 通过卤代烃的亲核取代反应合成了一种含二硫键的脂肪族二元醇（DSU），将其以硬段形式引入到聚氨酯分子中，制备了一系列二硫键改性的聚氨酯复合材料。通过核磁确定了DSU的化学结构，采用万能电子试验机、扫描电子显微镜等测试了DSU用量对聚氨酯的压缩力学性能、水接触角、微观形貌和黏接强度等性能的影响。结果表明，当DSU用量为改性蓖麻油多元醇的10 wt.%时，材料表现出较好的综合性能，骨黏接强度为0.97 MPa，压缩强度为7.0 MPa，压缩模量为41.3 MP，新鲜兔血液中骨黏接强度为0.49 MPa。体外大鼠骨髓间充质干细胞培养实验表明，材料具有良好的细胞相容性，其多孔结构有利于细胞的增殖和黏附，有望应用于医用骨胶黏剂领域。Abstract: Aliphatic diol HO-(CH2)6-S-S-(CH2)6-OH (DSU) containing disulfide bond was synthesized by the nucleophilic substitution reaction of halohydrocarbon, which was introduced into polyurethane molecules in the form of hard segment. A series of polyurethane composites modified by disulfide bond were prepared by using methylene diphenyl diisocyanate (MDI), dopamine modified castor oil and DSU as raw materials, and their structures and properties were optimized. The chemical structure of DSU was characterized by NMR, and the influence of the amount of DSU on polyurethane were investigated, including the compressive mechanical properties, water contact angle, microstructure and bone bonding strength. The main conclusions include that the compressive properties and hydrophobicity of polyurethane composites increased with the increase of DSU dosage, and the bone adhesion strength increased first and then decreased. As the DSU content increased to 10 wt.% of modified castor oil, the composites presented the best comprehensive properties with the bone adhesion strength of 0.97 MPa in the buffer solution and 0.49 MPa in rabbit blood, compression strength of 7.0 MPa, compression modulus of 41.2 MPa and average bubble size of 150 μm. In vitro culture experiments of rat bone marrow mesenchymal stem cells showed that the polyurethane composites had excellent cytocompatibility. The cell staining results by Calcein-AM showed that the porous structure of the material was conducive to cell proliferation and adhesion, which was in favour of fracture healing and reconstruction. This new material prepared in this work is expected to be used in the field of medical bone adhesives.
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Key words:
- polyurethane /
- bone adhesive /
- disulfide bond /
- biocompatibility
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图 1 HO―(CH2)6―S―S―(CH2)6―OH(DSU)的合成
Figure 1. The synthesis of diols containing a disulfide bond (DSU)
图 2 6-溴-1-己醇(左图)和HO―(CH2)6―S―S―(CH2)6―OH(右图)的1H-NMR谱图
Figure 2. The 1H-NMR spectra of 6-bromo-1-hexanol and DSU
图 3 DSU含量对聚氨酯力学性能的影响：a）压缩强度，b）压缩模量
Figure 3. The effect of DSU content on the compressive property of polyurethane adhesives: a) compressive strength and b) compressive modulus
图 4 不同DSU含量下聚氨酯SEM图：a） PU-DSU-0, b） PU-DSU-5, c） PU-DSU-10, d） PU-DSU-15, e） PU-DSU-20
Figure 4. SEM topographies of polyurethane adhesives with different DSU content: a) PU-DSU-0, b) PU-DSU-5, c) PU-DSU-5, d) PU-DSU-15, e) PU-DSU-20
图 5 不同DSU含量下聚氨酯胶黏剂水接触角
Figure 5. Water contact angle of polyurethane adhesives with different DSU content
图 6 不同DSU含量下聚氨酯胶黏剂骨黏接强度
Figure 6. The bone bonding strength of polyurethane adhesives with different DSU content
图 7 PU-DSU-10在不同浓度GSH溶液中的降解曲线
Figure 7. The degradation of PU-DSU-10 in GSH solutions with different concentration
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