CN113518804B - 一种用于3d打印的墨水材料、制备方法及用途 - Google Patents
一种用于3d打印的墨水材料、制备方法及用途 Download PDFInfo
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Abstract
本发明涉及一种用于3D打印的墨水、制备方法及墨水的用途。该墨水是由α玉米醇溶蛋白,玉米蛋白重量0‑0%的制孔剂,乙醇和水组成的凝胶。该制备方法包括:把10~50%重量的玉米醇溶蛋白溶解在含有40~90%(v/v)乙醇的水溶液中,加入玉米蛋白重量0‑10%的制孔剂,在5~95℃恒温静置1~10天或者搅拌30分钟‑24小时后,获得可用于3D打印的墨水材料。该方法条件温和、操作简单,所述的3D打印的墨水的力学性能和生物相容性好。可用于生物医学领域,在室温下3D打印制备组织工程替代物和止血材料。
Description
技术领域
本发明属于生物制造领域,涉及一种可用于3D打印的墨水材料、制备方法及墨水的用途。
背景技术
3D打印技术是近年来兴起的一项新兴制造技术,是根据计算机辅助设计,或者通过影像诊断仪如CT断层扫描仪获得数据后再输出到3D打印机,用打印墨水精确3D堆积、快速制造既定形状的3D数字化成型技术。迄今为止,能够用于3D打印的材料有合成高分子(如:聚乳酸(PLA)、聚己内酯(PCL))、天然高分子(如:明胶、胶原蛋白、壳聚糖、海藻酸钠、纤维素)和无机材料(如羟基磷灰石、磷酸三钙)。天然高分子材料具有优良的生物相容性、可降解性和可在较低温度下打印等特点。但因力学性能差使其应用受到了限制。寻找新的基于天然高分子材料的生物墨水是3D打印领域亟待解决的问题。
玉米醇溶蛋白已被证明在组织工程领域具有应用潜力,如用传统的模压成型法制备的三维多孔支架具有优良的细胞相容性和力学性能,能用于骨缺损修复。开发可3D打印的玉米醇溶蛋白墨水将极大地推动该材料在生物医学工程领域更为广泛的应用。经检索,仅有一篇会议论文与之相关(ESAFORM 2016:Proceedings of the 19th InternationalEASFORM Conference on Material Forming),该工作采用玉米蛋白与增塑剂甘油混合后作为墨水,在130℃温度下进行打印。该温度下的玉米蛋白呈现热塑性质,对其生物相容性和降解性能均有不良影响。本发明提供可用于3D打印的玉米蛋白墨水,可在温和条件下进行3D打印,不仅不会影响玉米蛋白的结构和性质,而且利于维持细胞和活性因子活性。
发明内容
本发明要解决的问题是:提供一种用于3D打印的墨水材料。
本发明要解决的另一问题是:提供上述用于3D打印的墨水材料的制备方法。
本发明要解决的第三个问题是:提供上述3D打印墨水的用途。
本发明的用于3D打印的墨水是由α玉米醇溶蛋白组成的凝胶,该凝胶可以在室温下进行3D打印。具体的说,该凝胶是含有10~50%(w/v)的α玉米醇溶蛋白的乙醇和水混合溶液形成的凝胶,所述的乙醇和水混合溶液与α玉米醇溶蛋白是体积与重量之比,例如,100ml乙醇和水混合溶液中含有α玉米醇溶蛋白10-50克。推荐该α玉米醇溶蛋白凝胶中含有30~50%重量的α玉米醇溶蛋白。所述的乙醇和水混合溶液中,乙醇和水的体积比为40~90:10~60。推荐醇和水的体积比为60~85:15~40。
本发明所述的用于3D打印的墨水材料的制备方法是通过以下步骤实现的:把10~50%玉米醇溶蛋白溶解在乙醇和水的混合溶液中,在5~95℃下,推荐10-50℃下,静置反应1~10天,推荐1-3天,或者在此温度下将上述的10~50%玉米醇溶蛋白溶解在乙醇和水的混合溶液,搅拌反应30分钟-24小时后获得用于3D打印的墨水。推荐采用搅拌方法,使墨水性能更加可控,制得可用于3D打印的墨水材料;所述的混合溶液中,乙醇和水的体积比为40~90:10~60。所述的制备方法中,优先采用室温下制备;还可以通过在制得的墨水中加入制孔剂的方法调整打印产品的孔结构和孔隙率,推荐加入量为玉米醇溶蛋白质量的0-10%w/w。所述的制孔剂甘露醇、碳酸氢铵、氯化钠、酒石酸钠和柠檬酸钠等水溶性物质或糖的颗粒,也可用石蜡颗粒或冰颗粒等周知的制孔剂。
利用本发明提供的3D打印墨水,可用于生物医学领域,包括:将影像诊断仪如CT断层扫描仪所获数字化数据通过3D打印机精准、快速制造既定形状;3D打印高分辨、内部孔隙结构和机械性能可控的组织工程替代物以及止血材料。如:管状产品(如神经导管、气管、尿道管和血管等)、膜状产品(如人造皮肤和止血膜材料)、3D支架产品(如骨、软骨、耳朵、止血材料)。支架孔隙率30-95%;压缩强度0.2MPa至20MPa、压缩模量10MPa至300MPa;弯曲强度0.5MPa至18MPa、弯曲模量15至100MPa;拉伸强度0MPa至2MPa、拉伸模量0MPa至20MPa。凝胶状墨水还可不打印,通过注射或涂抹方式直接用于深层且伤口不规则的贯穿伤止血、或者与3D打印产品协同止血,以及组织渗漏的封堵,该墨水材料零剪切粘度30-5000Pa·s,推荐120-4000Pa·s。止血机理分为以下步骤:先是凝胶中所含乙醇的释放导致凝胶固化的同时沉淀了血液中的蛋白成分;然后是吸附大量血小板;最后纤维蛋白原浓缩成为纤维蛋白、捕获红血球等血球细胞。
利用本发明提供的上述可用于3D打印的墨水打印出的产品可以是由一个3D打印机喷头打印出α玉米醇溶蛋白单一组分产品,也可以是由两个或多个3D打印机喷头打印出α玉米醇溶蛋白和其它墨水材料(包括:合成和天然高分子如聚乳酸、海藻酸钠、羧甲基纤维素钠、明胶等)混合的多组分产品。
本发明的用于3D打印的玉米蛋白墨水,原料丰富,制备方法简便。而且可在室温条件下进行3D生物打印,不会影响玉米蛋白的结构和性质,利于维持细胞和活性因子活性。
附图说明
图1:实施例2制备的α玉米醇溶蛋白凝胶状3D打印墨水材料。
图2:实施例3制备的α玉米醇溶蛋白墨水经3D打印出的组织工程管状产品。
图3:实施例4制备的α玉米醇溶蛋白墨水经3D打印出的网格型止血膜材料,黑色表示网格的孔结构。
图4:利用实施例4所述止血膜材料对皮肤出血的止血效果图。
图5:实施例7制备的α玉米醇溶蛋白墨水经3D打印出的各种形状3D产品。
图6:实施例8制备的α玉米醇溶蛋白墨水经3D打印出含细胞的组织工程人工耳。刚打印出时为凝胶态人工耳(左图),右图为固化后人工耳。
图7:利用实施例7所述多孔止血材料及实施例9制备的α玉米醇溶蛋白凝胶材料协同作用于贯穿伤模型的止血效果图。
具体实施方式
下面通过实施例对本发明进行具体描述,以下实例只用于对本发明进行进一步说明,不能理解为对本发明保护范围的限制。在阅读了本发明内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书的范围。
实施例1
一种可用于3D打印的墨水材料,由以下质量份数的原料制成:α玉米醇溶蛋白10g。
本实施例的可用于3D打印的墨水材料的制备方法,步骤如下:
将α玉米醇溶蛋白溶解在100mL体积分数为含有40%乙醇的水溶液中,经室温超声处理10min,得到乳白色溶液。然后,将该溶液置于10℃静置反应10天,得到可用于3D打印的墨水材料,该墨水材料零剪切粘度约28Pa·s。
实施例2
一种可用于3D打印的墨水材料,由以下质量份数的原料制成:α玉米醇溶蛋白20g。
本实施例的可用于3D打印的墨水材料的制备方法,步骤如下:
将α玉米醇溶蛋白溶解在100mL体积分数为含有65%乙醇的水溶液中,经室温超声处理10min,得到透明溶液。然后,将该溶液置于20℃静置反应1天,得到可用于3D打印的墨水材料,为凝胶状,如图1所示。该墨水材料零剪切粘度约120Pa·s。
实施例3
一种可用于3D打印的墨水材料,由以下质量份数的原料制成:α玉米醇溶蛋白30g。
本实施例的可用于3D打印的墨水材料的制备方法,步骤如下:将α玉米醇溶蛋白溶解在100mL体积分数为70%的乙醇水溶液中,经室温超声处理10min,得到透明溶液。然后,将该溶液置于30℃静置反应2天,得到可用于3D打印的墨水材料,该墨水材料零剪切粘度约389Pa·s。
利用本实施例制得的墨水材料,与制孔剂甘露醇颗粒(占玉米蛋白质量的6%,w/w)混合后,装入打印喷头中,利用直径0.5mm打印针头,在10℃、打印速度8mm/s、打印压力150kPa条件下,室温3D打印出管状产品,水煮法除去制孔剂后得到多孔管状产品。如图2所示,可作为组织工程神经导管等。
实施例4
一种可用于3D打印的墨水材料,由以下质量份数的原料制成:α玉米醇溶蛋白40g。
本实施例的可用于3D打印的墨水材料的制备方法,步骤如下:将α玉米醇溶蛋白溶解在100mL体积分数为80%的乙醇水溶液中,经室温超声处理10min,得到透明溶液。然后,将该溶液置于40℃静置反应4天,得到可用于3D打印的墨水材料,该墨水材料零剪切粘度约1832Pa·s。利用直径0.33mm打印针头,在20℃、打印速度8mm/s、打印压力80kPa条件下,3D打印出网格型膜状产品,如图3所示,用作止血膜材料。图4是利用该止血膜材料对大鼠皮肤出血的止血效果图。
实施例5
一种可用于3D打印的墨水材料,由以下质量份数的原料制成:α玉米醇溶蛋白50g。
本实施例的可用于3D打印的墨水材料的制备方法,步骤如下:将α玉米醇溶蛋白溶解在100mL体积分数为85%的乙醇水溶液中,经室温超声处理10min,得到透明溶液。然后,将该溶液置于50℃静置反应8天,得到可用于3D打印的墨水材料,该墨水材料零剪切粘度约1623Pa·s。
实施例6
一种可用于3D打印的墨水材料,由以下质量份数的原料制成:α玉米醇溶蛋白20g。
本实施例的可用于3D打印的墨水材料的制备方法,步骤如下:将α玉米醇溶蛋白溶解在100mL体积分数为90%的乙醇水溶液中,经室温超声处理10min,得到透明溶液。然后,将该溶液置于10℃搅拌12小时,得到可用于3D打印的墨水材料,该墨水材料零剪切粘度约55Pa·s。
实施例7
一种可用于3D打印的墨水材料,由以下质量份数的原料制成:α玉米醇溶蛋白30g。
本实施例的可用于3D打印的墨水材料的制备方法,步骤如下:将α玉米醇溶蛋白溶解在100mL体积分数为65%的乙醇水溶液中,经室温超声处理10min,得到透明溶液。然后,将该溶液置于20℃搅拌30分钟,得到可用于3D打印的墨水材料,该墨水材料零剪切粘度约344Pa·s。打印针头尺寸为0.5mm,在50℃、打印速度8mm/s、打印压力200kPa条件下,3D打印出组织工程替代物。图5是用本实施例墨水材料打印出的各种尺寸3D材料,可以看出,玉米醇溶蛋白墨水材料适用于打印3D支架产品。支架压缩强度3.34±1.25MPa、压缩模量63.93±19.22MPa;弯曲强度5.30±1.32MPa、弯曲模量52.07±11.07MPa;拉伸强度0.11±0.02MPa、拉伸模量2.63±1.25MPa,与松质骨匹配。
实施例8
一种可用于3D打印的墨水材料,由以下质量份数的原料制成:α玉米醇溶蛋白30g。
本实施例的可用于3D打印的墨水材料的制备方法,步骤如下:将α玉米醇溶蛋白溶解在100mL体积分数为85%的乙醇水溶液中,经室温超声处理10min,得到透明溶液。然后,将该溶液置于30℃搅拌6小时,得到可用于3D打印的墨水材料,该墨水材料零剪切粘度约551Pa·s。
在第一打印喷头中装入上述可用于3D打印的墨水材料,在第二打印喷头中装入混有细胞的海藻酸钠(细胞密度1*106个/ml)墨水材料,在37℃,利用直径0.33mm打印针头,打印速度8mm/s、打印压力80kPa条件下3D打印出组织工程器官,图6为打印出的人工耳。该墨水材料可单独或与细胞或其它墨水材料混合,3D打印出不规则形状的组织工程替代物。
实施例9
一种可用于3D打印的墨水材料,由以下质量份数的原料制成:α玉米醇溶蛋白50g。
本实施例的可用于3D打印的墨水材料的制备方法,步骤如下:将α玉米醇溶蛋白溶解在100mL体积分数为90%的乙醇水溶液中,经室温超声处理10min,得到透明溶液。然后,将该溶液置于50℃搅拌4小时,得到凝胶墨水材料。该凝胶材料零剪切粘度约3476Pa·s,可通过注射或涂抹方式用于深层且伤口不规则的贯穿伤止血,也可与3D打印产品共同使用(图7)。
Claims (11)
1.一种用于3D打印的墨水,其特征是:所述的墨水是α玉米醇溶蛋白、乙醇和水混合而成的凝胶,其零剪切粘度为30-5000Pa·s;打印温度是室温。
2.如权利要求1所述的用于3D打印的墨水,其特征在于:该α玉米醇溶蛋白凝胶中含有10~50%重量的α玉米醇溶蛋白,还含有玉米蛋白重量0-10%的制孔剂,其余为体积计数的乙醇和水;乙醇和水的体积比为40~90:10~60。
3.如权利要求2所述的用于3D打印的墨水,其特征在于:所述的制孔剂为甘露醇、碳酸氢铵、氯化钠、酒石酸钠、柠檬酸钠、糖的颗粒或石蜡颗粒。
4.如权利要求2所述的用于3D打印的墨水,其特征在于:该α玉米醇溶蛋白凝胶中含有30~50%的α玉米醇溶蛋白。
5.如权利要求2所述的用于3D打印的墨水,其特征在于:所述的乙醇和水的体积比为60~85:15~40。
6.一种如权利要求1所述的用于3D打印的墨水的制备方法,其特征在于是通过以下步骤实现的:把10~50%玉米醇溶蛋白溶解在乙醇和水的混合溶液中,在5~95℃下,恒温静置反应1~10天,或者搅拌反应30分钟-24小时后,制得可用于3D打印的墨水材料,再加入玉米蛋白重量0-10%的制孔剂;所述的混合溶液中,乙醇和水的体积比为40~90:10~60。
7.如权利要求6所述的一种用于3D打印的墨水的制备方法,其特征在于所述的静置反应温度为10~50℃,静置反应1~3天。
8.如权利要求1所述的一种用于3D打印的墨水的用途,其特征在于制备生物医用材料。
9.如权利要求8所述的一种用于3D打印的墨水的用途,其特征在于所述的3D打印产品为管状、膜状、3D支架的组织工程替代物或止血材料。
10.如权利要求9所述的一种用于3D打印的墨水的用途,其特征在于所述的组织工程替代物是神经导管、人造气管、人造尿道管、人造血管、人造皮肤、止血膜材料、人造骨、人造软骨、人造耳朵。
11.如权利要求10所述的一种可用于3D打印的墨水的用途,其特征在于所述的止血材料是用于深层且伤口不规则的贯穿伤止血材料或协同止血的材料。
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