CN113082297B - 一种超顺磁性骨修复材料的制备方法 - Google Patents
一种超顺磁性骨修复材料的制备方法 Download PDFInfo
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- CN113082297B CN113082297B CN202110405414.2A CN202110405414A CN113082297B CN 113082297 B CN113082297 B CN 113082297B CN 202110405414 A CN202110405414 A CN 202110405414A CN 113082297 B CN113082297 B CN 113082297B
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- sodium tripolyphosphate
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Abstract
本发明提供了一种超顺磁性骨修复材料的制备方法,步骤如下:(1)制备超顺磁性纳米四氧化三铁,(2)制备纳米三聚磷酸钙钠,(3)用相对平均分子量不同的三种或者三种以上乳酸/羟基乙酸共聚物混合在一起包覆纳米四氧化三铁和纳米三聚磷酸钙钠,制备超顺磁性骨修复材料。所述乳酸/羟基乙酸共聚物相对平均分子量在2×103和8×105之间。随着树脂降解,三聚磷酸钙钠被释放出来。低分子量树脂降解速度快,随后较高分子量的树脂陆续降解,三聚磷酸钙钠也被陆续释放出来。这样能够满足在较宽的时间段内被释放出的三聚磷酸钙钠维持较稳定的释出量。良好的磁学性能和生物相容性、能够诱导骨组织形成的能力使其可以作为骨修复材料使用。
Description
技术领域
本发明涉及一种超顺磁性骨修复材料的制备方法,具体涉及用乳酸/羟基乙酸共聚物包覆纳米四氧化三铁(Fe3O4)和纳米三聚磷酸钙钠的方法。
背景技术
在生物体中,多聚磷酸盐主要存在于骨组织的成骨细胞中,是成骨细胞的重要成分,发挥着调节钙化过程的功能。人工合成的多聚磷酸盐与天然骨组织的多聚磷酸盐具有相似性,可以作为聚磷酸盐生物复合物的基础。
聚乳酸具有生物降解性,与人体相容性也好,在体内可以完全降解并被吸收,可以作为骨折内固定材料,用于骨组织工程支架的制备。但聚乳酸的骨结合能力不足。我们知道,如果没有钙和磷,骨骼系统的功能是不可能发挥的,而充足的钙离子和磷酸根离子有利于骨骼生长、合成和修复。文献中研究表明,向聚乳酸中引入骨性结合组分是提高聚乳酸骨结合能力的有效途径。其中,羟基磷灰石和磷酸三钙具有良好的生物降解性、生物相容性、骨诱导能力,在人体中降解下来的钙、磷能进入活体的循环系统形成新骨,因此作为骨性结合组分研究和应用最为广泛。与聚乳酸复合之后,可以获得各种预期性能的固定复合材料。除羟基磷灰石和磷酸三钙外,三聚磷酸钙钠的元素组成(Ca和P)与天然骨组织中的多聚磷酸盐相似,与骨组织具有相容性,同时在体液中溶解度低,也可作为组织替代材料的可吸收成分。
发明内容
本发明的目的正是为了提供一种在使役期内骨修复材料能够稳定地释放三聚磷酸钙钠的超顺磁性骨修复材料的制备方法。
本发明的目的可通过下述技术措施来实现:
本发明的超顺磁性骨修复材料的制备方法步骤如下:
(1)制备超顺磁性纳米四氧化三铁:
(1-1)在聚四氟乙烯内衬的水热反应釜中将三氯化铁溶解到乙二醇中,然后加入尿素和有机酸盐,搅拌溶解,得到反应液;其中三氯化铁、尿素、有机酸盐与乙二醇的重量比是0.5~5: 0.5~5:0.2~1.5:100;
(1-2)将分散剂加入到乙二醇中,加热搅拌至分散剂全部溶解,得到分散剂溶液,其中分散剂浓度1%~10%;
(1-3)取占反应液质量1/5~1/3的分散剂溶液,加入到反应液中,控制水热反应温度160℃~210℃,反应时间6h~12h;降至室温,取出反应液,用磁铁进行固液分离,用去离子水反复冲洗至中性;
(2)制备纳米三聚磷酸钙钠:
(2-1)将氯化钙、氨基酸、乙二胺四乙酸二钠一起溶于水中配成水溶液,其中氯化钙浓度为1%~30%,氨基酸和乙二胺四乙酸二钠浓度均为0.05%~3.0%;
(2-2)配制浓度为5%~30%的三聚磷酸钠水溶液,然后按照Ca:Na物质的量比2:0.9~1.1的量将三聚磷酸钠水溶液滴加到步骤(2-1)中的水溶液中,滴加耗时不少于1小时,滴加完毕后静置6小时以上;
(2-3)加入乙醇使纳米三聚磷酸钙钠从水溶液中沉淀出来,然后用水反复冲洗至中性;
(3)制备超顺磁性骨修复材料:
(3-1)按重量比1:0.1~10取超顺磁性纳米四氧化三铁和纳米三聚磷酸钙钠,加入到水中,其中纳米粒子与水的重量比为1:10~100;超声波辅助分散,形成纳米粒子分散液;
(3-2)将乳酸/羟基乙酸共聚物溶于二氯甲烷中形成均匀溶液,浓度在1%~70%之间;所述乳酸/羟基乙酸共聚物是三种或者三种以上不同相对平均分子量乳酸/羟基乙酸共聚物的混合物,所述乳酸/羟基乙酸共聚物的相对平均分子量在2×103和8×105之间,所述乳酸/羟基乙酸共聚物中乳酸链节和羟基乙酸链节的物质的量比为1: 0.9~1.1;
(3-3)按照体积比1:1~20,将步骤(3-1)中纳米粒子分散液加入到步骤(3-2)中的二氯甲烷溶液中,分散成稳定乳液;
(3-4)将上述稳定乳液加入到浓度为0.5%~3%的聚乙烯醇水溶液中,所述乳液与聚乙烯醇水溶液的体积比为1:2~20,搅拌,形成乳液;
(3-5)旋转蒸发除去乳液中二氯甲烷,用磁铁沉降树脂颗粒,并用水洗涤沉淀,真空冷冻干燥,得到超顺磁性骨修复材料;所述超顺磁性骨修复材料颗粒粒径小于2微米。
本发明中所述有机酸盐取自三水乙酸钠、酒石酸钠或柠檬酸钠中的任意一种。
所述分散剂取自聚乙二醇、聚乙烯吡咯烷酮、Tween系列非离子表面活性剂或Span系列非离子表面活性剂中的任意一种或两种及两种以上的组合。
所述氨基酸取自天冬氨酸、谷氨酸或甘氨酸的任意一种或两种及两种以上的组合。
进一步说,超顺磁性四氧化三铁(Fe3O4)纳米颗粒是一种多功能的磁性材料,在生物医药方面有广泛应用。磁性四氧化三铁纳米颗粒制备工艺简单,对细胞无毒,体内稳定,而且可以很容易地在其表面包覆生物高分子如聚糖、蛋白质等,形成核壳结构,也赋予其生物相容性,在外加磁场的作用下具有靶向性。因此,本发明在骨修复材料中引入超顺磁性四氧化三铁。
步骤(1)的目的是制备纳米级的超顺磁四氧化三铁。与大粒径的超顺磁四氧化三铁相比,超顺磁纳米颗粒的剩磁和矫顽力基本上趋于零,颗粒间只存在很微弱的磁偶极作用,能形成稳定的磁性流体。
步骤(2)的目的是采用有机模板法制备纳米三聚磷酸钙钠。有机模板中的活性基团(COOH,NH2,OH基团)是聚磷酸盐颗粒的结晶中心,有机模板的化学结构和浓度决定着聚磷酸盐的组成、粒径大小等。尽管明胶、多肽和蛋白质都可以作为模板用于纳米聚磷酸盐的制备,基于溶解度、毒性和与生物体的相容性等多种因素,本发明中使用具有生物学意义的脂肪族氨基酸作为有机模板,即天冬氨酸、谷氨酸、甘氨酸,所制备的三聚磷酸钙钠粒径为5-100nm。Ca2+能与氨基酸的COOH和NH2基团反应,形成络合物。所形成的络合物稳定性差,加入三聚磷酸钠会形成三聚磷酸钙钠沉淀。乙二胺四乙酸二钠有助于纳米结构的稳定和分散,也可以调节纳米颗粒中Ca的含量。乙二胺四乙酸二钠与Ca2+形成的稳定络合物,可以用水冲洗除去。
步骤(3)中将乳酸/羟基乙酸共聚物包覆在纳米四氧化三铁和纳米三聚磷酸钙钠表面,得到聚乳酸/纳米四氧化三铁/纳米三聚磷酸钙钠超顺磁性骨修复材料,可以用于激光选区烧结制备组织工程支架等。在体内树脂降解会释放出三聚磷酸钙钠,最终参与到骨骼生长、合成和修复等活动中。
本发明的有益效果如下:
本发明所述生物降解型树脂是乳酸和羟基乙酸的共聚物。在相同条件下,树脂的降解速度与其组成有关,譬如聚乳酸的降解速度慢,聚羟基乙酸的速度快,而乳酸/羟基乙酸共聚物的降解速度则在两者之间。同样是乳酸/羟基乙酸共聚物,如果两种链节的含量比发生变化,共聚物的降解速度也会发生改变。乳酸/羟基乙酸链节物质的量比为1:1的共聚物降解速度最快,7天可以完全降解。
树脂的降解速度还与分子量有关。分子量低则降解速度快,分子量大则降解速度慢。本发明中乳酸/羟基乙酸共聚物是三种或者三种以上相对平均分子量不同的乳酸/羟基乙酸共聚物的混合物。所述乳酸/羟基乙酸共聚物相对平均分子量均在2×103和8×105之间。使役前期时低分子量树脂降解,中期时中等分子量树脂降解,后期时高分子量树脂降解,这样就在整个使役期内树脂颗粒的降解比较平稳,相应地三聚磷酸钙钠也被较为匀速地释放出来。这样在较宽的时间段内被释放出的三聚磷酸钙钠维持着较稳定的释出量,有利于钙和磷被充分吸收和利用。如果单独使用一种相对平均分子量的乳酸/羟基乙酸共聚物,较低和较高分子量的树脂含量少,中等分子量的树脂占大部分。这样前期和后期树脂总的降解速度慢,释放出的三聚磷酸钙钠少,造成三聚磷酸钙钠的量不足,而使役中期树脂总的降解速度快,释放出的三聚磷酸钙钠多,但过多的三聚磷酸钙钠并不能完全被利用。
另外,树脂的降解速度还与树脂颗粒粒径有关。对于大粒径的乳酸/羟基乙酸共聚物树脂颗粒,内部树脂降解速度大于表面树脂降解速度,而对于小粒径颗粒,内部树脂的降解速度和表面的降解速度几乎一样。因此,在本发明中采用复乳法工艺,能使树脂颗粒粒径保持在2微米以下。
按照上述技术方案,可以得到颗粒规整度高、粒径在2微米以下的超顺磁性骨修复材料,具有良好的磁学性能和生物相容性,能够诱导骨组织形成。
具体实施方式
本发明以下将结合实施例作进一步描述:
实施例1
(1)制备超顺磁性纳米四氧化三铁
将15g六水三氯化铁溶解到500g乙二醇中,高速搅拌,形成淡黄色透明溶液;加入20g尿素和4g三水乙酸钠,搅拌至均匀后得到反应液。
配制浓度为8%的聚乙二醇(PEG-400)溶液,取130g加入到反应液中,搅拌均匀后,加入到水热反应器中,控制温度200℃,保温反应10h。将反应液温度降至室温,把反应液转移到容器中,用磁铁进行固液分离,用去离子水反复冲洗至中性。采用透射电子显微技术检测,平均粒径23nm;磁强计测量,饱和磁场强度53.9emu/g。
(2)制备纳米三聚磷酸钙钠
称取50g氯化钙、1g天冬氨酸、1g乙二胺四乙酸二钠溶于1000mL水中;搅拌均匀后,磁力搅拌下滴加400mL浓度为21%的三聚磷酸钠水溶液,1小时滴加完毕。然后,密闭容器,静置12小时。
磁力搅拌下缓慢加入乙醇,出现浑浊之后再继续加入200mL乙醇。静置,待沉降完全后倾去上层清液。用去离子水冲洗,直至中性。采用透射电子显微技术检测,平均粒径42nm。
(3)制备超顺磁性骨修复材料
取步骤(1)中四氧化三铁2g和步骤(2)中三聚磷酸钙钠3g加入到200mL水中,超声波辅助分散,形成稳定内水相。
分别取相对平均分子量1×104、8×104、1×105的乳酸/羟基乙酸(50/50)共聚物8g、6g、4g,一起溶于800mL二氯甲烷中,形成稳定油相。
把内水相加入到油相中,均质器分散30min,12000r/min,形成稳定初乳。
取初乳50mL,滴加到500mL浓度为1%的聚乙烯醇水溶液中,1.5小时内滴加完毕,滴加的同时进行机械搅拌,转速500r/min,形成乳液。滴加完毕后继续搅拌2小时。旋转蒸发除去二氯甲烷,然后取出,用磁铁沉降树脂颗粒,并用500mL水分多次进行洗涤,真空冷冻干燥,得到超顺磁性骨修复材料。采用透射电子显微技术检测,平均粒径171nm;磁强计测量,饱和磁场强度0.11emu/g。
实施例2
(1)制备超顺磁性纳米四氧化三铁
将15g六水三氯化铁溶解到500g乙二醇中,高速搅拌,形成淡黄色透明溶液;加入15g尿素和5g酒石酸钠,搅拌至均匀后得到反应液。
配制浓度为8%的聚乙二醇(PEG-400)溶液,取130g加入到反应液中,搅拌均匀后,加入到水热反应器中,控制温度200℃,保温反应10h。将反应液温度降至室温,把反应液转移到容器中,用磁铁进行固液分离,用去离子水反复冲洗至中性。采用透射电子显微技术检测,平均粒径38nm;磁强计测量,饱和磁场强度61.1emu/g。
(2)制备纳米三聚磷酸钙钠
称取60g氯化钙、1g天冬氨酸、1g乙二胺四乙酸二钠溶于1000mL水中;搅拌均匀后,磁力搅拌下滴加400mL浓度为25%的三聚磷酸钠水溶液,1小时滴加完毕。然后,密闭容器,静置12小时。
磁力搅拌下缓慢加入乙醇,出现浑浊之后再继续加入200mL乙醇,静置,待沉降完全后倾去上层清液。用去离子水冲洗,直至中性。采用透射电子显微技术检测,平均粒径59nm。
(3)制备超顺磁性骨修复材料
取步骤(1)中四氧化三铁1.5g和步骤(2)中三聚磷酸钙钠4g加入到200mL水中,超声波辅助分散,形成稳定内水相。
分别取相对平均分子量5×103、2×104、2×105的乳酸/羟基乙酸(50/50)共聚物4g、7g、7g,一起溶于800mL二氯甲烷中,形成稳定油相。
把内水相加入到油相中,均质器分散30min,12000r/min,形成稳定初乳。
取初乳50mL,滴加到500mL浓度为1.5%的聚乙烯醇水溶液中,1.5小时内滴加完毕,滴加的同时进行机械搅拌,转速500r/min,形成乳液。滴加完毕后继续搅拌2小时。旋转蒸发除去二氯甲烷,然后取出,用磁铁沉降树脂颗粒,并用500mL水分多次进行洗涤,真空冷冻干燥,得到超顺磁性骨修复材料。采用透射电子显微技术检测,平均粒径184nm;磁强计测量,饱和磁场强度0.08emu/g。
Claims (4)
1.一种超顺磁性骨修复材料的制备方法,特征在于:所述制备方法的步骤如下:
(1)制备超顺磁性纳米四氧化三铁:
(1-1)在聚四氟乙烯内衬的水热反应釜中将三氯化铁溶解到乙二醇中,然后加入尿素和有机酸盐,搅拌溶解,得到反应液;其中三氯化铁、尿素、有机酸盐与乙二醇的重量比是0.5~5: 0.5~5:0.2~1.5:100;
(1-2)将分散剂加入到乙二醇中,加热搅拌至分散剂全部溶解,得到分散剂溶液,其中分散剂浓度1%~10%;
(1-3)取占反应液质量1/5~1/3的分散剂溶液,加入到反应液中,控制水热反应温度160℃~210℃,反应时间6h~12h;降至室温,取出反应液,用磁铁进行固液分离,用去离子水反复冲洗至中性;
(2)制备纳米三聚磷酸钙钠:
(2-1)将氯化钙、氨基酸、乙二胺四乙酸二钠一起溶于水中配成水溶液,其中氯化钙浓度为1%~30%,氨基酸和乙二胺四乙酸二钠浓度均为0.05%~3.0%;
(2-2)配制浓度为5%~30%的三聚磷酸钠水溶液,然后按照Ca:Na物质的量比2:0.9~1.1的量将三聚磷酸钠水溶液滴加到步骤(2-1)中的水溶液中,滴加耗时不少于1小时,滴加完毕后静置6小时以上;
(2-3)加入乙醇使纳米三聚磷酸钙钠从水溶液中沉淀出来,然后用水反复冲洗至中性;
(3)制备超顺磁性骨修复材料:
(3-1)按重量比1:0.1~10取超顺磁性纳米四氧化三铁和纳米三聚磷酸钙钠,加入到水中,其中纳米粒子与水的重量比为1:10~100;超声波辅助分散,形成纳米粒子分散液;
(3-2)将乳酸/羟基乙酸共聚物溶于二氯甲烷中形成均匀溶液,浓度在1%~70%之间;所述乳酸/羟基乙酸共聚物是三种或者三种以上不同相对平均分子量乳酸/羟基乙酸共聚物的混合物,所述乳酸/羟基乙酸共聚物的相对平均分子量在2×103和8×105之间,所述乳酸/羟基乙酸共聚物中乳酸链节和羟基乙酸链节的物质的量比为1: 0.9~1.1;
(3-3)按照体积比1:1~20,将步骤(3-1)中纳米粒子分散液加入到步骤(3-2)中的二氯甲烷溶液中,分散成稳定乳液;
(3-4)将上述稳定乳液加入到浓度为0.5%~3%的聚乙烯醇水溶液中,所述乳液与聚乙烯醇水溶液的体积比为1:2~20,搅拌,形成乳液;
(3-5)旋转蒸发除去乳液中二氯甲烷,用磁铁沉降树脂颗粒,并用水洗涤沉淀,真空冷冻干燥,得到超顺磁性骨修复材料;所述超顺磁性骨修复材料颗粒粒径小于2微米。
2.根据权利要求1所述的超顺磁性骨修复材料的制备方法,特征在于:所述有机酸盐取自三水乙酸钠、酒石酸钠或柠檬酸钠中的任意一种。
3.根据权利要求1所述的超顺磁性骨修复材料的制备方法,特征在于:所述分散剂取自聚乙二醇、聚乙烯吡咯烷酮、Tween系列非离子表面活性剂或Span系列非离子表面活性剂中的任意一种或两种及两种以上的组合。
4.根据权利要求1所述的超顺磁性骨修复材料的制备方法,特征在于:所述氨基酸取自天冬氨酸、谷氨酸或甘氨酸的任意一种或两种及两种以上的组合。
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