CN116459386A - 一种载银纳米二氧化钛修饰聚多巴胺光热抗菌型水凝胶及其制备方法 - Google Patents
一种载银纳米二氧化钛修饰聚多巴胺光热抗菌型水凝胶及其制备方法 Download PDFInfo
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- CN116459386A CN116459386A CN202310329892.9A CN202310329892A CN116459386A CN 116459386 A CN116459386 A CN 116459386A CN 202310329892 A CN202310329892 A CN 202310329892A CN 116459386 A CN116459386 A CN 116459386A
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Abstract
本发明公开了一种载银纳米二氧化钛修饰聚多巴胺光热抗菌型水凝胶及其制备方法，该水凝胶为Gel‑PAM/PDA@Ag/TiO2，其中Gel‑PAM为水凝胶骨架，具有互穿型双网络；PDA@Ag/TiO2均匀分布于水凝胶网络中；所述PDA@Ag/TiO2是载银纳米二氧化钛Ag/TiO2吸附于PDA颗粒而形成的纳米颗粒。本发明通过蓝光源可精准操控水凝胶靶点原位成型，安全便捷；PDA@Ag/TiO2的引入不仅增强了水凝胶的机械性能，还使其具有高的光热转化效率，在近红外光(808nm)的辐射下，5min就可迅速灭杀99％以上的大肠杆菌与金黄色葡萄球菌。
Description
技术领域
本发明属于生物医用敷料领域，涉及一种载银纳米二氧化钛修饰聚多巴胺光热抗菌型水凝胶及其制备方法。
背景技术
内窥镜治疗后的出血、穿孔等并发症会导致免疫保护功能降低，造成诸多潜在的威胁。愈合过程中，易受到多种细菌微生物的侵扰，引发炎症反应，延缓创面的恢复。传统可注射水凝胶在其内部掺杂抗菌物质(抗生素、富勒烯)来抵御细菌的入侵，短期虽有不错的治疗效果，但是抗生素的过度使用与其潜在的毒性仍是一个隐患。将小分子的抗菌药物接枝于天然生物高分子可以使敷料具备持续、稳定的抑菌能力，此方法制备的止血敷料虽然具备长久有效的抗菌性能，但是如何采用精准可控的方法，短时间内快速高效的杀死大量有害细菌仍是一个需要解决的难题。
纳米颗粒(NPs)是近年来备受关注的一种抗菌材料，它对细菌感染部位具有靶向能力，可以精准灭菌。在基于NPs的治疗中，光热疗法(PTT)在促进创面愈合方面有着很大的应用前景。具有光响应的敷料在特定波长光的照射下，局部伤口的温度会迅速升高，在短时间内就可杀死大量细菌，副作用少且安全性高。聚多巴胺(PDA)具有良好的光稳定性、生物相容性及生物降解性，是一种有前途的光热剂。然而，PDA光热转化效率较低，表面存在的多种活性基团(如儿茶酚、伯胺等)使其在制备过程中易于团聚，不仅增加了PDA的粒径，而且导致光吸收效率变差，光热转化效率降低。此外，肠胃道内环境复杂，对可注射水凝胶的机械性能有着很高的要求，进行注射操作时往往需要制定详细的计划，估算靶点凝胶成型时间，这无疑增加了注射风险。
发明内容
本发明解决的技术问题在于提供一种载银纳米二氧化钛修饰聚多巴胺光热抗菌型水凝胶及其制备方法，通过蓝光可快速制备可注射水凝胶，无需估算靶点凝胶成型时间。
本发明是通过以下技术方案来实现：
一种载银纳米二氧化钛修饰聚多巴胺光热抗菌型水凝胶，该水凝胶为Gel-PAM/PDA@Ag/TiO2，其中Gel-PAM为水凝胶骨架，具有互穿型双网络；PDA@Ag/TiO2均匀分布于水凝胶网络中；
所述PDA@Ag/TiO2是载银纳米二氧化钛Ag/TiO2吸附于PDA颗粒而形成的纳米颗粒。
水凝胶Gel-PAM/PDA@Ag/TiO2是将PDA@Ag/TiO2置于水凝胶前驱液中，在蓝光照射后快速成型；
其中，水凝胶前驱液均封装于注射器中。
所述的水凝胶前驱液包括PDA@Ag/TiO2、明胶、丙烯酰胺、交联剂、六水合三(2,2-联吡啶)氯化钌和过硫酸铵；
其中，水凝胶前驱液中PDA@Ag/TiO2的质量百分比为1～2％、丙烯酰胺的质量百分比为20～30％、明胶的质量百分比为5～10％、六水合三(2,2-联吡啶)氯化钌与过硫酸铵的质量百分比均为0.01～0.02％。
所述交联剂为N,N’-亚甲基双丙烯酰胺，其质量为丙烯酰胺的1～3‰。
一种载银纳米二氧化钛修饰聚多巴胺光热抗菌型水凝胶的制备方法，包括以下操作：
1)PDA@Ag/TiO2的制备：
以去离子水与无水乙醇作为溶剂，滴加氨水后于室温下磁力搅拌；然后缓慢加入溶于去离子水中的盐酸多巴胺，混合溶液后继续反应24h；反应结束后使用去离子水洗涤并离心，收集PDA纳米颗粒；
将PDA纳米颗粒加入去离子水中磁力搅拌，然后滴加入Ag/TiO2，继续搅拌10h；反应结束后离心，收集得到PDA@Ag/TiO2颗粒；
2)Gel-PAM/PDA@Ag/TiO2的制备：
将PDA@Ag/TiO2置于明胶、丙烯酰胺、交联剂、六水合三(2,2-联吡啶)氯化钌和过硫酸铵组成的反应液中形成水凝胶前驱液；
水凝胶前驱液中PDA@Ag/TiO2的质量百分比为1～2％、丙烯酰胺的质量百分比为20～30％、明胶的质量百分比为5～10％、六水合三(2,2-联吡啶)氯化钌与过硫酸铵的质量百分比均为0.01～0.02％；
然后使用452nm的蓝光照射10～15s后得到Gel-PAM/PDA@Ag/TiO2水凝胶。
在蓝光的照射下，水凝胶前驱液中六水合三(2,2-联吡啶)氯化钌被过硫酸铵快速氧化，生成Ru(III)和硫酸盐自由基；Ru(III)高效催化明胶中酪氨酸单元的酚羟基发生偶联，在数秒内构建Gel网络；此同时，硫酸盐自由基引发AAm和MBA发生自由基聚合，形成了互穿型双网络水凝胶，这个过程中PDA@Ag/TiO2会均匀分散于网络内部。
所述的载银纳米二氧化钛修饰聚多巴胺光热抗菌型水凝胶作为抑菌、止血的注射水凝胶的应用。
与现有技术相比，本发明具有以下有益的技术效果：
本发明提供的载银纳米二氧化钛修饰聚多巴胺光热抗菌型水凝胶，通过聚多巴胺的粘附能力在其表面吸附载银纳米二氧化钛颗粒(PDA@Ag/TiO2)，将其置于水凝胶前驱液中蓝关照射后钌催化明胶链段酚羟基彼此交联，丙烯酰胺发生自由基聚合，快速形成三维互穿型水凝胶(Gel-PAM/PDA@Ag/TiO2)，PDA@Ag/TiO2则均匀分布于水凝胶网络；以聚丙烯酰胺和明胶为聚合物网络骨架，通过蓝光照射，在10s内迅速成型可注射水凝胶。借助注射器与蓝光源可在靶点原位成胶，精准可控；本发明操作简单，通过蓝光源可精准操控水凝胶靶点原位成型，安全便捷，无需估算靶点凝胶成型时间。
本发明提供的载银纳米二氧化钛修饰聚多巴胺光热抗菌型水凝胶，对猪皮、玻璃、塑料等基材均展现出良好的粘附力，单位面积内对猪皮组织的粘附强度高达73.2kPa。PDA@Ag/TiO2的引入不仅增强了水凝胶的机械性能，还使其具有高的光热转化效率，在近红外光(808nm)的辐射下，5min就可迅速灭杀99％以上的大肠杆菌与金黄色葡萄球菌。流变测试与拉伸实验显示，该水凝胶机械性能优异，最大拉伸长度可至原长的7.5倍，在不同的频率与应变下均可保持稳定。所制备的水凝胶生物粘附性优异，单位面积内对猪皮组织的最大粘附强大高达73.2kPa，远强于现有可注射水凝胶，媲美生物胶水。
本发明提供的载银纳米二氧化钛修饰聚多巴胺光热抗菌型水凝胶，Ag/TiO2的引入提升了PDA的光热转化效率，近红外光照射下，Gel-PAM/PDA@Ag/TiO2的最终温度(61.2℃)较Gel-PAM/PDA高出12℃；在相同时间、相同功率的近红外光照射下Gel-PAM/PDA@Ag/TiO2灭菌效果要远远强于Gel-PAM/PDA，表明Ag/TiO2与PDA的协同作用有效的增强了材料的光热转化效率；
本发明提供的载银纳米二氧化钛修饰聚多巴胺光热抗菌型水凝胶，在无近红外光照射(808nm)时，可以在短时间内(5min)迅速杀死99％以上的大肠杆菌和金黄色葡萄球菌；在无近红外光照射时，得益于银离子的抗菌性，Gel-PAM/PDA@Ag/TiO2仍然具备持续、稳定的抑菌效果。
附图说明
图1-1、图1-2分别为本发明的PDA与PDA@Ag/TiO2的透射电镜谱图；
图2为本发明的水凝胶在蓝光照射下快速成型示意图；
图3为本发明的水凝胶快速成型示意图；
图4为本发明的水凝胶的形貌示意图；
图5为本发明的水凝胶的溶胀率示意图；
图6为本发明的水凝胶的注射成型示意图；
图7为本发明的水凝胶的流变性能恢复示意图；
图8为本发明的水凝胶的粘附性示意图；
图9为本发明的水凝胶的光热转换图；
图10为本发明的水凝胶近红外光下三次循环的温度变化示意图；
图11为本发明的水凝胶的溶血率(图a)和凝血率粘附性(图b)示意图；
图12为本发明的水凝胶近红外光照射下抑菌效果，其中图a和图b为对大肠杆菌的抑菌效果，图c和图d为对金黄色葡萄球菌的的抑菌效果。
具体实施方式
以下实施例是对本发明的进一步说明，但本发明并不局限于此。
本发明提供一种载银纳米二氧化钛修饰聚多巴胺光热抗菌型水凝胶，该水凝胶为Gel-PAM/PDA@Ag/TiO2，其中Gel-PAM为水凝胶骨架，具有互穿型双网络；PDA@Ag/TiO2均匀分布于水凝胶网络中；
所述PDA@Ag/TiO2是载银纳米二氧化钛Ag/TiO2吸附于PDA颗粒而形成的纳米颗粒。
水凝胶Gel-PAM/PDA@Ag/TiO2是将PDA@Ag/TiO2置于水凝胶前驱液中，在蓝光照射后快速成型；
其中，水凝胶前驱液均封装于注射器中。借助注射器与蓝光源可在靶点原位成胶，精准可控；本发明操作简单，通过蓝光源可精准操控水凝胶靶点原位成型，安全便捷，无需估算靶点凝胶成型时间。
本发明的载银纳米二氧化钛修饰聚多巴胺光热抗菌型水凝胶的制备方法，包括以下操作：
1)PDA@Ag/TiO2的制备：
以去离子水与无水乙醇作为溶剂，滴加氨水后于室温下磁力搅拌；然后缓慢加入溶于去离子水中的盐酸多巴胺，混合溶液后继续反应24h；反应结束后使用去离子水洗涤并离心，收集PDA纳米颗粒；
将PDA纳米颗粒加入去离子水中磁力搅拌，然后滴加入Ag/TiO2，继续搅拌10h；反应结束后离心，收集得到PDA@Ag/TiO2颗粒；
2)Gel-PAM/PDA@Ag/TiO2的制备：
将PDA@Ag/TiO2置于明胶、丙烯酰胺、交联剂、六水合三(2,2-联吡啶)氯化钌和过硫酸铵组成的反应液中形成水凝胶前驱液；
水凝胶前驱液中PDA@Ag/TiO2的质量百分比为1～2％、丙烯酰胺的质量百分比为20～30％、明胶的质量百分比为5～10％、六水合三(2,2-联吡啶)氯化钌与过硫酸铵的质量百分比均为0.01～0.02％；
然后使用452nm的蓝光照射10～15s后得到Gel-PAM/PDA@Ag/TiO2水凝胶。
在蓝光的照射下，水凝胶前驱液中六水合三(2,2-联吡啶)氯化钌被过硫酸铵快速氧化，生成Ru(III)和硫酸盐自由基；Ru(III)高效催化明胶中酪氨酸单元的酚羟基发生偶联，在数秒内构建Gel网络；此同时，硫酸盐自由基引发AAm和MBA发生自由基聚合，形成了互穿型双网络水凝胶，这个过程中PDA@Ag/TiO2会均匀分散于网络内部。
本发明提供的载银纳米二氧化钛修饰聚多巴胺光热抗菌型水凝胶，在无近红外光(808nm)照射时，可以在短时间内(5min)迅速杀死99％以上的大肠杆菌和金黄色葡萄球菌；在无近红外光照射时，得益于银离子的抗菌性，Gel-PAM/PDA@Ag/TiO2仍然具备持续、稳定的抑菌效果。所述的载银纳米二氧化钛修饰聚多巴胺光热抗菌型水凝胶可作为抑菌、止血的注射水凝胶进行应用。
下面给出具体的制备实施例。
Gel-PAM/PDA@Ag/TiO2水凝胶的制备，包括以下操作：
1)载银纳米二氧化钛修饰聚多巴胺(PDA@Ag/TiO2)的制备
将90mL去离子水与40mL无水乙醇转移至圆底烧瓶中，缓缓滴加氨水2mL，28-30％)，室温下磁力搅拌30min；然后将0.5g盐酸多巴胺(DA)溶于10mL去离子水中，缓慢加入混合溶液后继续反应24h；待反应结束后使用去离子水洗涤三次并离心(15000rpm，10min)收集聚多巴胺(PDA)纳米颗粒。
将PDA纳米颗粒(4mL，10mg/mL)加入100mL去离子水中磁力搅拌30min，然后将Ag/TiO2(0.25mL，10wt％)滴加至混合液继续搅拌10h。反应结束后离心(15000rpm，10min)收集即为PDA@Ag/TiO2。
wt％为质量百分比。
图1-1、图1-2为PDA与PDA@Ag/TiO2的透射电镜谱图，对比发现光滑的PDA表面吸附了许多细小颗粒，表明Ag/TiO2吸附于PDA颗粒上。
2)Gel-PAM/PDA@Ag/TiO2水凝胶的制备
室温下，将10mgPDA@Ag/TiO2置于烧杯，加入适量去离子水使其均匀分散，制备1wt％PDA@Ag/TiO2分散液。
室温下，将0.4g丙烯酰胺加入到PDA@Ag/TiO2分散液，搅拌均匀，使其质量百分比为20％；然后再加入0.1g明胶，均匀搅拌，使其质量百分比为5％；再加入N,N’-亚甲基双丙烯酰胺(丙烯酰胺的千分之一)、六水合三(2,2-联吡啶)氯化钌(0.01wt％)、过硫酸铵(0.01wt％)搅拌均匀，得到水凝胶前驱液。
室温下，使用452nm蓝光源照射10s，得到目标水凝胶Gel-PAM/PDA@Ag/TiO2。
图2为水凝胶由液态到凝胶态的转变，图3展示了蓝光照射下水凝胶仅需10s就可完成溶胶到凝胶的转变。
下面对Gel-PAM/PDA@Ag/TiO2水凝胶的各项性能进行说明。
1)水凝胶的形貌与溶胀
如图4所示，Gel-PAM/PDA@Ag/TiO2水凝胶的内部结构为多孔结构，所有孔径大小均一，如同蜂窝状。三维多孔结构具有优异的机械性能，良好的减震性与吸湿性，其结构交错复杂，多成对称分布；多孔结构有利于液体的吸收，为伤口提供湿润的环境，利于细胞的生长增殖，不会对其造成压迫损伤。
AgNPs由于其高比表面积被广泛应用于抗菌剂，但是银离子过高时，会造成细胞的死亡与组织的炎症反应。而TiO2可以很好抑制银离子的大量流出，降低生物毒性。此外在可见光的照射下，电子与空穴分离，界面电荷转移到Ag纳米颗粒上，抑制电子空穴重组，延长Ag/TiO2体系中电子和空穴的寿命。元素映射谱图显示了Ti与Ag均匀的分布于水凝胶表面，与组织相互作用时可持续、缓慢的流出，不会造成局部离子浓度过高。元素能谱(EDX)分析显示，C、O为水凝胶内部主要元素，而Ti(0.51％)与Ag(0.09％)含量均不超过0.2％。
Gel-PAM、Gel-PAM/PDA、Gel-PAM/Ag/TiO2与Gel-PAM/PDA
@Ag/TiO2水凝胶的溶胀性能如图5所示，其中Gel-PAM的溶胀率最大(492％)，而Gel-PAM/PDA@Ag/TiO2的溶胀率最低(428％)，这是由于PDA@Ag/TiO2的引入使得水凝胶交联程度变高，因此溶胀率降低。
2)水凝胶的可注射性
医用可注射水凝胶的制备过程复杂，形成时间为5-30min，治疗过程中应严格控制注射时间，对医生的操作有着极大的考验，有着一定的风险。如何在靶点快速、精准的控制水凝胶形成是巨大的挑战。如图6所示，将Gel-PAM/PDA@Ag/TiO2水凝胶前驱液注入注射器，作用于目标位置，完成注射后使用452nm蓝光灯源照射，令人惊喜的是Gel-PAM/PDA@Ag/TiO2前驱液受到蓝光照射后可迅速从溶胶状态转变至凝胶(10s)。使用动态旋转流变仪对其进行了流变恢复实验(图7所示)，施加应变小于临界应变时，其储能模量一直大于损耗模量，维持着凝胶状态。
当施加应变大于临界应变时，出现了剪切变稀现象，Gel-PAM/PDA@Ag/TiO2转变为溶胶状态，60s后施加应变再次小于临界应变，重新恢复为凝胶状态。其储能模量与损耗模量与未施加应变前相比没有明显的改变，实验表明Gel-PAM/PDA@Ag/TiO2在受到短暂的外力破坏时，仍可恢复其形态，具有长久的使用寿命。
3)水凝胶的粘附性
粘附性强的止血敷料可与组织紧密贴合，抵御微生物的侵扰，同时为伤口提供舒适环境。Gel与PDA中含有大量的酚羟基，聚丙烯酰胺网络中含有酰胺，与肌肤组织中的氨基、羧基形成氢键，在过硫酸铵的催化氧化下，部分酚羟基被氧化为活性醌，与-NH2与-SH发生席夫碱反应与1,4-迈克尔加成反应，因此Gel-PAM/PDA@Ag/TiO2具有强粘附性。
以猪皮为模拟组织，分别评测了四种水凝胶对皮肤组织的粘附性，如图8所示，Gel-PAM/PDA@Ag/TiO2的粘附性能最优，高达73.2kPa，远强于现有可注射水凝胶，媲美生物胶水。
粘附后在经过抖动、晃动时，Gel-PAM/PDA@Ag/TiO2仍可以牢牢吸附，不发生脱落，这是因为在溶胶状态下网络内的高分子为圆形粒子，慢慢渗入了被粘附物体的表面空隙内，在蓝光的照射下，溶胶迅速转变为凝胶状态，基材表面水分减少，高分子体依靠相互间的拉力，使两种材料紧密粘合。
4)水凝胶的光热性能
近红外光热转化是指水凝胶在吸收近红外光后，经表面区域等离子体共振效应将光能转化为电子或空穴谐振的动能、或者电子跃迁产生能量，通过晶格散射的振动能，像环境传递从而使环境升温的现象。Ag/TiO2在PDA的表面吸附生长后具备了PDA的特性，因此PDA@Ag/TiO2有出色的光热转化能力。
对比Gel-PAM、Gel-PAM/PDA、Gel-PAM/Ag/TiO2与Gel-PAM/PDA
@Ag/TiO2四种水凝胶在近红外光(808nm)照射下的光热转换能力。实验激光所用功率为1.5W/cm-2，照射时长为5min，每隔30s记录一次光热图像与实时温度。
如图9所示，Gel-PAM与Gel-PAM/Ag/TiO2温度变化较小，最高温度只能升至38℃附近，没有光热转化能力。而Gel-PAM/PDA水凝胶相比于Gel-PAM和GelPAM/Ag/TiO2，温度上升速度有了明显的提升，最高可至49.2℃。在相同的时间内，GelPAM/PDA@Ag/TiO2温度可以上升至61.2℃，与Gel-PAM/PDA相比提高了12℃，具有出色的光热转化效率。这是因为Ag/TiO2在近红外光照射时与PDA呈协同作用，增强了PDA的光热转化能力，与文献10min的照射时长对比，Gel-PAM/PDA@Ag/TiO2升温迅速，安全高效。
如图10所示，对PAM/PDA@Ag/TiO2实施了三个循环的近红外光照射，每次间隔5min，第三次近红外光照时水凝胶温度仍可达到62.5℃，证明该敷料的光热转化能力是可重复利用的，且升温速率恒定。在不断经过近红外光的照射后，PAM/PDA@Ag/TiO2的含水量降低，导热系数增加，因此第三次循环后的温度较最初测试时有所上升。
5)水凝胶的血液相容性与体外凝血性能
溶血实验是评价生物相容性的重要手段之一，国际标准ISO10993-4规定止血敷料的溶血率应小于5％，否则将造成红细胞的大量破损，血红蛋白逸出，引发溶血现象。
如图11的a图所示，Gel-PAM、Gel-PAM/PDA、Gel-PAM/Ag/TiO2与Gel-PAM/PDA@Ag/TiO2四种水凝胶的溶血率分别为1.5％，1.8％，2.1％，2.3％，金属纳米粒子的引入造成少量红细胞的破损，但均符合国际标准ISO 10993-4，证明四种止血敷料都具有优异的血液相容性。
止血是创面恢复四个过程(伤口止血、急性炎症、细胞增值、组织重塑)的第一步，因此材料的止血性能至关重要。Gel-PAM/PDA@Ag/TiO2为三维多孔结构，具有良好的溶胀性能，粘附于创面时可以起到压迫止血的效果，并吸收血液、周围渗出体液。此外水凝胶中的明胶含有正电子附着物和精氨酸-甘氨酸-冬氨酸(RGD)肽序列，不仅可以启动内源与外源的止血途径，而且有利于血小板的吸附，并在局部形成小血栓，当血栓范围增大时就可起到止血效果。对四种水凝胶的凝血率(BCI)进行了测定，与对照相比，BCI越低表明在相同的时间内材料促进血液凝固的性能越强，Gel-PAM、Gel-PAM/PDA、GelPAM/Ag/TiO2与Gel-PAM/PDA@Ag/TiO2的凝血率分别为33.4％，32.9％，35.3％，35.1％，均具有出色的凝血效果(图11的b图所示)。
6)水凝胶的抗菌性
光热抗菌(PTT)是一种新型的抗菌疗法，光敏材料或光敏剂(PDA、CNTs、AgNPs)可吸收光转化为热，提高组织的温度。照射时会引起蛋白质变性、细胞空化破裂、气泡形成、DNA碎裂，从而对靶点的有害微生物、细胞等进行热消融，达到令人满意的治疗效果。高特异性和低风险性使得PTT成为极具潜力的治疗方法，它可以加速伤口区域的血液流动，同时刺激成纤维细胞增殖和减少炎症，从而加速伤口愈合过程。
本发明对照Gel-PAM/PDA、Gel-PAM/Ag/TiO2与Gel-PAM/PDA
@Ag/TiO2三种水凝胶在近红外光的照射下对大肠杆菌和金黄色葡萄球菌的抗菌性。如图12的图a、图b所示，在近红外光(808nm)的照射下，Gel-PAM/PDA与Gel-PAM/PDA@Ag/TiO2对大肠杆菌的抑菌率分别78％和99.5％，而Gel-PAM/Ag/TiO2在近红外光的照射下没有表现出抑菌性能，没有表现出光热抗菌效果，大肠杆菌的菌落数量几乎没有发生改变。
对于金黄色葡萄球菌，Gel-PAM/PDA与Gel-PAM/PDA@Ag/TiO2的抑菌率分别为58％和99％，这与大肠杆菌的结果类似(图12的图d、图d所示)。
对比发现，在相同时间、相同功率的近红外光照射下Gel-PAM/PDA@Ag/TiO2灭菌效果要远远强于Gel-PAM/PDA。表明Ag/TiO2与PDA的协同作用有效的增强了材料的光热转化效率；近红外光照射5min后，Gel-PAM/PDA@Ag/TiO2最终温度可达61℃，而Gel-PAM/PDA的最终温度仅为49.2℃，不足以消灭全部的细菌。
以上给出的实施例是实现本发明较优的例子，本发明不限于上述实施例。本领域的技术人员根据本发明技术方案的技术特征所做出的任何非本质的添加、替换，均属于本发明的保护范围。
Claims (7)
1.一种载银纳米二氧化钛修饰聚多巴胺光热抗菌型水凝胶，其特征在于，该水凝胶为Gel-PAM/PDA@Ag/TiO2，其中Gel-PAM为水凝胶骨架，具有互穿型双网络；PDA@Ag/TiO2均匀分布于水凝胶网络中；
所述PDA@Ag/TiO2是载银纳米二氧化钛Ag/TiO2吸附于PDA颗粒而形成的纳米颗粒。
2.如权利要求1所述的载银纳米二氧化钛修饰聚多巴胺光热抗菌型水凝胶，其特征在于，水凝胶Gel-PAM/PDA@Ag/TiO2是将PDA@Ag/TiO2置于水凝胶前驱液中，在蓝光照射后快速成型；
其中，水凝胶前驱液均封装于注射器中。
3.如权利要求2所述的载银纳米二氧化钛修饰聚多巴胺光热抗菌型水凝胶，其特征在于，所述的水凝胶前驱液包括PDA@Ag/TiO2、明胶、丙烯酰胺、交联剂、六水合三(2,2-联吡啶)氯化钌和过硫酸铵；
其中，水凝胶前驱液中PDA@Ag/TiO2的质量百分比为1～2％、丙烯酰胺的质量百分比为20～30％、明胶的质量百分比为5～10％、六水合三(2,2-联吡啶)氯化钌与过硫酸铵的质量百分比均为0.01～0.02％。
4.如权利要求3所述的载银纳米二氧化钛修饰聚多巴胺光热抗菌型水凝胶，其特征在于，交联剂为N,N’-亚甲基双丙烯酰胺，其质量为丙烯酰胺的1～3‰。
5.一种载银纳米二氧化钛修饰聚多巴胺光热抗菌型水凝胶的制备方法，其特征在于，包括以下操作：
1)PDA@Ag/TiO2的制备：
以去离子水与无水乙醇作为溶剂，滴加氨水后于室温下磁力搅拌；然后缓慢加入溶于去离子水中的盐酸多巴胺，混合溶液后继续反应24h；反应结束后使用去离子水洗涤并离心，收集PDA纳米颗粒；
将PDA纳米颗粒加入去离子水中磁力搅拌，然后滴加入Ag/TiO2，继续搅拌10h；反应结束后离心，收集得到PDA@Ag/TiO2颗粒；
2)Gel-PAM/PDA@Ag/TiO2的制备：
将PDA@Ag/TiO2置于明胶、丙烯酰胺、交联剂、六水合三(2,2-联吡啶)氯化钌和过硫酸铵组成的反应液中形成水凝胶前驱液；
水凝胶前驱液中PDA@Ag/TiO2的质量百分比为1～2％、丙烯酰胺的质量百分比为20～30％、明胶的质量百分比为5～10％、六水合三(2,2-联吡啶)氯化钌与过硫酸铵的质量百分比均为0.01～0.02％；
然后使用452nm的蓝光照射10～15s后得到Gel-PAM/PDA@Ag/TiO2水凝胶。
6.如权利要求5所述的一种载银纳米二氧化钛修饰聚多巴胺光热抗菌型水凝胶的制备方法，其特征在于，在蓝光的照射下，水凝胶前驱液中六水合三(2,2-联吡啶)氯化钌被过硫酸铵快速氧化，生成Ru(III)和硫酸盐自由基；Ru(III)高效催化明胶中酪氨酸单元的酚羟基发生偶联，在数秒内构建Gel网络；此同时，硫酸盐自由基引发AAm和MBA发生自由基聚合，形成了互穿型双网络水凝胶，这个过程中PDA@Ag/TiO2会均匀分散于网络内部。
7.权利要求1所述的载银纳米二氧化钛修饰聚多巴胺光热抗菌型水凝胶作为抑菌、止血的注射水凝胶的应用。
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