CN115120779B - 一种可用于3d打印的水凝胶泡沫材料及其制备方法与应用 - Google Patents
一种可用于3d打印的水凝胶泡沫材料及其制备方法与应用 Download PDFInfo
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- CN115120779B CN115120779B CN202110295779.4A CN202110295779A CN115120779B CN 115120779 B CN115120779 B CN 115120779B CN 202110295779 A CN202110295779 A CN 202110295779A CN 115120779 B CN115120779 B CN 115120779B
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- foaming
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- agent
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Abstract
本发明属于3D打印和生物材料技术领域，公开了一种可用于3D打印的水凝胶泡沫材料及其制备方法、制备装置与应用。通过用生物相容性发泡剂和固化剂混合及初步发泡，然后与生物相容性可固化组分混合并进一步发泡，最后与细胞悬液混合均匀并预固化，即可用于3D生物打印。本发明所使用制备装置简单，操作简便，所制备的水凝胶泡沫材料具良好的生物相容性和可3D打印性，孔隙率高度可调并易于调节，与目前普遍的生物墨水相比，该材料有利于细胞的铺展生长以及营养物质和代谢废物的交换。不仅能够用于药物测试、仿生结构、组织修复和再生医学领域，还在多孔吸附材料、绝缘材料、减震缓冲材料、电容器的制备方面具有很大的应用前景。
Description
技术领域
本发明属于3D打印和生物材料技术领域，具体涉及一种可用于3D打印的水凝胶泡沫材料及其制备方法、制备装置与应用。
背景技术
3D生物打印是3D打印技术在生物医学领域的重要应用，具有高精度、高效率、个性化等特点，对促进药物研发、个性化医疗和再生医学的发展具有重大意义。
生物墨水作为3D生物打印的要素之一，已经被研究人员进行了深入的开发与研究。为了满足3D生物打印，生物墨水应该具备良好的生物相容性、打印保真度、可降解性、通透性，在打印的过程中和打印后具有合适的机械强度等。水凝胶材料因与天然组织相似，具有良好的生物材料特性，被广泛用于生物墨水的制备，主要包括天然水凝胶类生物墨水和合成水凝胶类墨水。
然而目前的生物墨水难以同时满足3D生物打印的要求，尤其是材料的通透性，不利于打印后细胞营养物质和代谢废物的交换，也不利于细胞在打印结构内的铺展和生长，从而导致所打印产品的性能受到很大的限制。因此，如何开发一种既能满足生物相容性、可打印性，又具有高的孔隙率和通透性的生物墨水显得尤为重要。
发明内容
本发明的主要目的在于提供一种可用于3D生物打印的水凝胶泡沫材料、其制备方法和应用，从而解决目前3D打印墨水中普遍存在的打印材料通透性不好、不利于细胞在三维空间中铺展和生长的问题。
为实现前述目的，本发明提供的一种可用于3D生物打印的水凝胶泡沫材料，包括以下组分：5%-8%生物相容性发泡剂、2%-5%生物相容性可固化组分、0.2%-0.5%固化剂、负载细胞，余量为溶剂，总质量为100%，上述百分数均为质量体积百分数。
所述的生物相容性发泡剂为明胶（gelatin）、卵清蛋白、普朗尼克F127（PluronicF127）中的至少一种。
所述的生物相容性可固化组分为海藻酸盐（alginate）、结冷胶（gellan gum）、胶原（collagen）、壳聚糖（chitosan）、甲基丙烯酰化明胶(GelMA)、明胶（gelatin）中的至少一种。
所述的固化剂为针对所使用的可固化组分的小分子离子交联剂。较佳地，针对海藻酸盐可选用硫酸钙（CaSO4），针对结冷胶可选用氯化钠（NaCl），针对胶原可选用碳酸氢钠（NaHCO3），针对壳聚糖可选用柠檬酸钠（NaCit），针对甲基丙烯酰化明胶可选用光固化剂，如光引发剂i2959（IRGACURE 2959，i2959）或光诱发剂LAP（Lithium phenyl-2,4,6-trimethylbenzoylphosphinate，LAP），针对明胶则是降温固化。
所述的负载细胞可为任意需要进行3D生物打印的细胞，或被溶剂代替从而进行无负载细胞的水凝胶泡沫材料的打印。
所述的溶剂为水、磷酸缓冲溶液、Hank's平衡盐溶液、细胞培养基中的至少一种。
较佳地，一种可用于3D生物打印的水凝胶泡沫材料的制备方法，其特征在于，该方法包括如下步骤：
（1）配制所需浓度的发泡剂和固化剂溶液，将一定体积的发泡剂、固化剂与一定体积的空气进行混合初步发泡；
（2）配制所需浓度的可固化组分溶液，并将一定体积的初步发泡得到的泡沫与一定体积的可固化组分使用上一步所述的发泡装置进行进一步混合发泡；
（3）准备好所需的细胞悬液，将一定体积的进一步发泡得到的泡沫与一定体积的细胞悬液均匀混合，并原位预固化，即得可用于3D生物打印的水凝胶泡沫材料。
本发明还提供一种简易的网格发泡装置。这种装置的特征在于：将2个带有鲁尔接头的注射器分别连接到内部含有网格片的鲁尔连接器两端，即可使用。较佳地，该网格发泡装置主要包括5个部分，由2个带有鲁尔接头的注射器、2个能通过螺纹连接起来的鲁尔连接头和1个网格片组成。将网格片放置于两个鲁尔接头螺纹连接处，两个接头通过螺纹连接起来，并把网格片固定于两个接头之间，得到带网格的鲁尔连接器，再把带有鲁尔接头的注射器分别连接到带网格的鲁尔连接器两端，即得该网格发泡装置。
与现有技术相比，本发明的有益效果是：
（1）本发明所用原料均具有优异的生物相容性，且较易得到，成本低廉，有利于本材料推广应用；
（2）本发明制备方法简单，节省时间；
（3）不需要模板直接进行多孔结构材料的3D打印，所打印的结构具有高的孔隙率、优异的通透性，打印的细胞能够长时间培养存活；
（4）本发明的水凝胶泡沫的孔隙率（空隙占比）高度可控。
附图说明
图1为使用本发明的实施例1所得的可用于3D生物打印的水凝胶泡沫打印的三维支架照片。
图2为本发明的实施例1所得的水凝胶泡沫光学显微镜照片。
图3为本发明的实施例1所得的水凝胶泡沫冻干扫描电子显微镜照片。
图4为细胞在本发明的实施例1所得的可用于3D生物打印的水凝胶泡沫打印的三维支架中与在同浓度普通海藻酸钠-明胶水凝胶中活性对比柱状图。
图5为细胞在本发明的实施例2所得的可用于3D生物打印的水凝胶泡沫打印的三维支架中生长并进行活死染色后的荧光显微镜照片。
图6为本发明提供的一种简易的网格发泡装置的示意图。
具体实施方式
下面通过具体的实施例对本发明的技术方案进行清楚、完整的描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。在不脱离本发明上述方法思想的情况下，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例（例如根据本领域普通技术知识和惯用手段做出的各种替换或变更），都属于本发明保护的范围。
实施例1
（1）将明胶溶解于细胞培养基中，得到12%明胶溶液，作为发泡剂。将明胶和海藻酸钠一起溶解于细胞培养基中，得到7%海藻酸钠可固化组分。将硫酸钙分散于水中得到16%过饱和硫酸钙溶液作为固化剂。另外配置含有0.2% CaCl2的细胞培养基备用；
（2）将0.6 mL发泡剂加到上述带鲁尔接头的注射器中，并加入50 µL固化剂，在另一个带鲁尔接头的注射器中设置3 mL空气；
（3）将两个注射器分别连接到上述带网格的鲁尔连接器两端，然后配合按压两端的注射器，让组分在发泡装置内充分混合并形成丰富的泡沫，一般地，这个过程需要进行来回50次；
（4）在其中一个注射器内保留1.5 mL初步发泡的泡沫，其余舍弃，在另一个注射器内加入1 mL可固化组分，两个注射器再次连接到带网格的鲁尔连接器两端，来回按压注射器，一般地，这个过程同样需要进行来回50次；
（5）在其中一个注射器内保留2 mL进一步发泡的泡沫，在另一个注射器内加入0.5mL A549细胞悬液，使用普通不带网格的鲁尔连接器连接两个注射器，然后使组分充分混合均匀；
（6）在室温下预固化10 min后转移到3D生物打印机中，设定好打印参数即可进行打印；
（7）打印后的高孔隙率材料在含有0.2% CaCl2的培养基中进行最后的固化和后续培养。
实施例2
当不需要负载细胞打印的时候，可以在实施例1的基础上直接省略与细胞悬液混合的步骤（5），并接着进行后面的操作，得到无细胞的泡沫材料或支架。
实施例3
（1）分别配置10%明胶作为发泡剂，8%明胶+6%海藻酸钠作为可固化组分，16%过饱和硫酸钙溶液作为固化剂，以及0.2% CaCl2备用；
（2）后续制备与打印方法与本发明实施例1中相同，得到水凝胶泡沫材料。
本发明提供的一种可用于3D生物打印的水凝胶泡沫材料，通过简单的装置和操作即可制备得到，不仅具有良好的生物相容性和可打印性，还具有高度可调节的孔隙率结构，满足不同细胞的生长需求。这种水凝胶泡沫材料不仅可以用于负载细胞用于药物测试、个性化治疗和组织工程，可以用于制备多孔结构的伤口辅料、吸水材料，还可以用于药物吸附和释放领域。本发明所提供的方法在多孔吸附材料、绝缘材料、减震缓冲材料、电容器的制备方面具有很大的应用前景。
Claims (3)
1.一种水凝胶泡沫在3D打印中的应用，其特征在于，所述水凝胶泡沫主体材料为生物相容性可固化组分和生物相容性发泡剂，通过在可固化组分中引入空气发泡，然后被固化剂预固化所得；
所述生物相容性可固化组分为海藻酸盐(alginate)、结冷胶(gellan gum)、胶原(collagen)、壳聚糖(chitosan)、甲基丙烯酰化明胶(GelMA)中的一种或任意几种；
所述的生物相容性发泡剂为明胶(gelatin)、卵清蛋白、普朗尼克F127(PluronicF127)中的一种或任意几种；
水凝胶泡沫的制备方法包括以下步骤：
(1)配制所需浓度的发泡剂和固化剂溶液，使用特制的发泡装置将一定体积的发泡剂、固化剂与一定体积的空气进行混合初步发泡；
(2)配制所需浓度的可固化组分溶液，并将一定体积的初步发泡得到的泡沫与一定体积的可固化组分使用上一步所述的发泡装置进行进一步混合发泡；
(3)准备好所需的细胞悬液，将一定体积的进一步发泡得到的泡沫与一定体积的细胞悬液均匀混合，并原位预固化，即得可用于3D生物打印的水凝胶泡沫材料。
2.根据权利要求1所述的水凝胶泡沫在3D打印中的应用，其特征在于，所述的固化剂为：针对海藻酸盐选用硫酸钙(CaSO4)，针对结冷胶选用氯化钠(NaCl)，针对胶原选用碳酸氢钠(NaHCO3)，针对壳聚糖选用柠檬酸钠(NaCit)，针对甲基丙烯酰化明胶选用光固化剂。
3.根据权利要求1所述的水凝胶泡沫在3D打印中的应用，其特征在于，所述的发泡剂、固化剂与空气的体积均可控制和改变，所述的初步发泡得到的泡沫与可固化组分的体积均可控制和改变，所述的进一步发泡得到的泡沫与细胞悬液的体积均可控制和改变。
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