CN116271202A - 快速自修复可注射纳米复合抗菌水凝胶敷料及其制备方法 - Google Patents
快速自修复可注射纳米复合抗菌水凝胶敷料及其制备方法 Download PDFInfo
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- CN116271202A CN116271202A CN202310138240.7A CN202310138240A CN116271202A CN 116271202 A CN116271202 A CN 116271202A CN 202310138240 A CN202310138240 A CN 202310138240A CN 116271202 A CN116271202 A CN 116271202A
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- acid
- hydrogel dressing
- rapid self
- injectable
- repairing
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Abstract
本发明公开了一种快速自修复可注射纳米复合抗菌水凝胶敷料及其制备方法，属于生物医用材料技术领域，包含以下步骤：（1）将双键封端的糖单体、两性离子、功能单体以及引发剂均匀混合于溶剂中，通入氮气鼓泡，将混合溶液升温进行聚合反应，得聚合产物，将粗产物在去离子水中常温下透析，并进行冷冻干燥得到聚合物；（2）将聚合物以溶解到在去离子水、PBS或生理盐水溶液中，加入含硼酸的硼羟基单体，然后通过超声将纳米粒子分散到上述混合溶液中，静置，得到快速自修复可注射纳米复合抗菌水凝胶敷料。本发明制备的水凝胶敷料具有快速的自愈能力和优异的注射性，以及良好的粘附性，对大肠杆菌和金黄色葡萄球菌具有有效的抗菌活性。
Description
技术领域
本发明涉及生物医用材料技术领域，特别涉及一种快速自修复可注射纳米复合抗菌水凝胶敷料及其制备方法。
背景技术
皮肤作为人体免疫系统的第一道防线，对维持正常的新陈代谢和信息交流至关重要。在日常生活中，由于受伤、烧伤、划伤或手术切口而形成的开放性伤口，不可避免地损害了皮肤的完整性。若没有适当的治疗，皮肤损伤可能会被微生物感染，导致慢性不愈合的伤口，甚至组织坏死。近年来，人们在开发各种类型的伤口敷料以加速伤口愈合过程方面做了大量工作，其中，水凝胶敷料因其在维持伤口湿润环境、吸收多余的渗出物和允许氧气渗透方面的优势被认为是伤口愈合敷料的理想选择。
自愈性的可注射水凝胶敷料，由于其能够覆盖不规则的伤口并适应身体频繁运动引起的变形，而受到广泛关注。然而，除了满足可恢复性和韧性等基本要求外，水凝胶伤口敷料如果在创伤处理过程中不具备抗菌性能，可能会导致微生物的感染及延长皮肤再生的过程。因此，具有抗菌活性的多功能水凝胶敷料能为愈合伤口提供额外的保护。
目前，将纳米颗粒抗菌剂通过物理封装或化学交联的方式加载入水凝胶基质中，为设计抗菌水凝胶敷料提供了有效的方案。尽管这些水凝胶在预防细菌感染方面有很大的吸引力，但多功能抗菌水凝胶的获得通常需要多阶段的修饰和复杂的设计，使其临床应用受限。因此，通过简便策略制备的多功能水凝胶伤口敷料在生物医学领域具有重要意义。
公告号为CN106492266B的专利公开了一种表面具有抗菌性纳米银/氧化锌复合水凝胶敷料的制备方法，用以制备具有良好抗菌性的水凝胶抗菌敷料。该发明的目的之二是运用溶解-再生的方法制备具有均一孔径的水凝胶载体。该发明的目的之三是将合成的水凝胶浸渍于一定浓度的硝酸银溶液中用紫外光照射，将Ag离子原位还原为粒径小的银纳米粒子均匀分布在水凝胶中，同时得到的银纳米粒子催化氧化锌纳米棒的生成，使纳米银和氧化锌棒在水凝胶上起到协同杀菌效果，提高水凝胶的抗菌性能。但是，该方法工艺制备复杂，制备时长较长。
公开号为CN111773429A的专利文献公开了一种水凝胶敷料及其制备方法和多功能纳米复合敷料及其制备方法和应用，涉及医用敷料技术领域。解决现有凝胶类敷料通常功能性单一、难以覆盖创口修复的全周期且抗菌性能较弱，难以达到令人满意的效果的技术问题。该敷料利用改性的壳聚糖和官能化的聚乙二醇构建了一种多功能的水凝胶敷料，该敷料具有良好的生物相容性、抗炎性、适当的皮肤粘附性和一定的止血性能，可以适应多种复杂的临床需要，在水凝胶敷料网状结构内搭载了光热纳米材料和抗菌药物，进而提供了一种多功能纳米复合敷料，提高了敷料的抗菌性能。然而，该多功能纳米复合敷料结构复杂，限制临床应用。
发明内容
有鉴于此，本发明的目的在于克服现有水凝胶敷料的缺点，提供了一种快速自修复可注射纳米复合抗菌水凝胶敷料及其制备方法，以解决现有技术中，水凝胶敷料愈合效果及生物相容性差等问题。
为解决上述技术问题，本发明所采取的技术方案是：
一种快速自修复可注射纳米复合抗菌水凝胶敷料的制备方法，包含以下步骤：
（1）将双键封端的糖单体、两性离子、功能单体以及引发剂均匀混合于溶剂中，通入氮气鼓泡10-60分钟，将混合溶液升温至65~80度下进行聚合反应，反应8~30小时，得聚合产物，将粗产物在去离子水中常温下透析1~3天，并进行冷冻干燥得到聚合物；
（2） 将聚合物以5~30wt%的浓度溶解到在去离子水、PBS或生理盐水溶液中，加入含硼酸的硼羟基单体1.0~10wt%，然后通过超声将纳米粒子0.1~10wt%分散到上述混合溶液中，静置10分钟，得到快速自修复可注射纳米复合抗菌水凝胶敷料。
进一步的，所述双键封端的糖单体结构是以下中的任意一种：
其中，R为以下结构中的任意一项：
进一步的，所述两性离子是：2-甲基丙烯酰氧乙基磷酸胆碱、磺基甜菜碱甲基丙烯酸酯、甲基丙烯酸羧酸甜菜碱 中的任意一种。
进一步的，所述功能单体是：N,N-二甲基丙烯酰胺、甲基丙烯酸羟乙酯、丙烯酸羟乙酯、甲基丙烯酸羟丙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸、丙烯酸、甲基丙烯酸缩水甘油酯、丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酰胺、丙烯酰胺、甲基丙烯酸2-氨基乙基酯盐酸盐、N-(3,4-二羟基苯乙基)甲基丙烯酰胺或3-(甲基丙烯酰氧)丙基三甲氧基硅烷中的任意一种。
进一步的，所述引发剂是：4,4'-偶氮双(4-氰基戊酸)、偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁酸二甲酯、过硫酸铵、过硫酸钾或过氧化苯甲酰中的任意一种。
进一步的，所述反应溶剂是去离子水、甲醇、乙醇、N,N-二甲基甲酰胺、乙二醇单甲醚、乙二醇单乙醚中的一种或几种的混合。
进一步的，所述纳米粒子是：银纳米粒子、金纳米粒子、二氧化钛粒子、氧化锌纳米粒子、铜纳米粒子、氧化铈纳米粒子、二氧化钛纳米粒子、硫化铜纳米粒子其中的一种或多种。
进一步的，所述含硼酸的硼羟基单体是：硼砂、苯硼酸、1,4-苯二硼酸、4-甲酯基苯硼酸、2-羟甲基苯硼酸、2-羟基苯硼酸、4-胺基苯硼酸、3-氨基苯硼酸、2-氨基苯硼酸、3-羟基苯硼酸、4-羟基苯硼酸、4-羟甲基苯硼酸、1,4-苯二硼酸、2-萘硼酸、4,4'-联苯基二硼酸、2-羟甲基苯基硼酸、2-羟甲基-5-氨基苯基硼酸、5-甲基丙烯酰胺基-1,2-苯并恶硼酮中的一种或多种。
进一步的，单体按重量和100%计算，双键封端的糖单体的含量为10 ~ 30 wt%，两性离子的含量为10 ~ 50 wt%，功能单体的含量为40-60 wt%。
进一步的，依据所述的快速自修复可注射纳米复合抗菌水凝胶敷料的制备方法得到的快速自修复可注射纳米复合抗菌水凝胶敷料。
进一步的，所述引发剂为总单体含量的1/1000~3/100；溶剂为总单体含量的2-5倍。
水凝胶是网络结构，一般由具有较大孔径和体积以及比表面积的交联亲水聚合物链组成的高分子材料。作为一种纳米抗菌剂，银纳米粒子（Ag NPs）因其出色的抗菌活性和避免耐药性的能力而成为潜在的替代物。目前，Ag NPs已被普遍通过物理封装或化学交联的方式加载到水凝胶敷料中，以防止伤口部位的感染并缩短愈合时间。抗菌水凝胶敷料因其在预防与伤口愈合相关的感染方面有前途的应用而受到广泛关注。然而，多功能抗菌水凝胶的设计不可避免地导致复杂的结构，这限制了它们的临床应用。
本发明的有益效果是：
从天然糖分子中获得的含有二醇的物质具有稳定的化学性质和良好的生物相容性等优点。改性后双键封端的糖单体，结构中的1，2-二醇容易与硼酸中的硼羟基形成动态硼酸酯键。基于动态硼酸酯键来设计制备具有自修复可注射抗菌水凝胶敷料是一种可行且有效的策略。
一、快速自修复可注射纳米复合抗菌水凝胶敷料整合了自愈合、注射性、抗菌、生物相容性等多功能，对其性能进行了研究。该纳米复合水凝胶对于大肠杆菌和金黄色葡萄球菌均有良好的抗菌效果。
二、聚合物链段中包含改性后的糖单体与两性离子，使得水凝胶具有优异的生物相容性；改性后的糖单体中1,2-二醇与含硼酸的硼羟基单体间形成的动态硼酸酯键赋予水凝胶快速的自愈能力；纳米颗粒在凝胶体系中的引入，使得复合水凝胶在伤口愈合的过程中能够抑制细菌滋生，促进伤口愈合；开发出兼具自修复、可注射、抗感染等多功能于一体的纳米复合水凝胶敷料，能够促进伤口愈合过程，在临床伤口愈合中具有潜在的应用价值。
三、该纳米复合水凝胶材料成本低，来源广，制备过程简便，是一种具备临床转化前景的抗菌水凝胶敷料。
本发明选取的原料具有优异的生物相容性，采用改性后的糖单体中1，2-二醇与含硼羟基单体之间的相互作用可提供快速的自愈过程，添加的纳米颗粒使水凝胶敷料具备良好的抗菌活性。采用该方法制得的水凝胶敷料具有快速自修复性、可注射性以及抗菌性能，能够用于皮肤受到创伤后的治疗。本发明不受加工条件精密程度的限制、制备方法简单、工艺条件温和、安全可靠、生物相容性和经济性更好。
附图说明
下面结合附图对本发明作进一步的详细说明。
图1 为本发明实施例1中的PMDL-12%/Borax/Ag NPs1.0水凝胶的扫描电镜示意图；
图2 本发明实施例1中的PMDL-12%/Borax/Ag NPs1.0水凝胶的可注射性能示意图；
图3 为本发明实施例1中的PMDL-12%/Borax/Ag NPs1.0水凝胶的自修复性能示意图；
图4 为本发明实施例1中的PMDL-12%/Borax/Ag NPs1.0水凝胶的流变性能测试；
图5为本发明实施例1中的PMDL-12%/Borax/Ag NPs1.0水凝胶的抗菌性能示意图；
图6为本发明实施例1中的PMDL-12%/Borax/Ag NPs1.0水凝胶与不同基底的粘附能力的示意图；
图7为本发明实施例1中的PMDL-12%/Borax/Ag NPs1.0水凝胶与新鲜猪皮的粘附能力的示意图。
实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例的附图1-7，对本发明实施例的技术方案进行清楚、完整地描述。显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例。基于所描述的本发明的实施例，本领域普通技术人员所获得的所有其他实施例，都属于本发明保护的范围。
实施例
共聚物的合成
将2-甲基丙烯酰氧乙基磷酸胆碱 (MPC)（88.6mg，0.3mmol），N,N-二甲基丙烯酰胺(DMA)（208.2mg，2.1mmol）和2-乳酰氨基乙基甲基丙烯酰胺(LAEMA)（281.1mg，0.6mmol）溶解在25 mL聚合管中的N,N-二甲基甲酰胺和去离子水的混合溶剂中，然后加入4,4'-偶氮双(4-氰基戊酸)（ACVA）（2.52mg，9.0μmol）并用氮气脱气30分钟。然后将聚合过程在70°C下搅拌24小时。共聚物通过针对H2O的透析纯化3天，然后冻干。所得共聚物P（MPC-DMA-LAEMA）命名为PMDL。采用傅里叶红外变换分光光度法（FT-IR）和以D2O为溶剂的1H NMR波谱对共聚物的组成进行了表征。该共聚物以ACVA为引发剂，通过MPC、DMA和LAEMA的自由基聚合得到。
水凝胶的制备和表征
水凝胶由共聚物PMDL、硼砂（Borax）和银纳米颗粒（Ag NPs）溶液简单混合而成。将共聚物PMDL以12% w / v浓度溶解在去离子水中并超声处理10 min，然后以4：1（v / v）的比例加入硼砂溶液（1.5%，w / v），并加入1.0% Ag NPs，命名为PMDL-12%/Borax/Ag NPs1.0水凝胶。
实施例
共聚物的合成
将2-甲基丙烯酰氧乙基磷酸胆碱 (MPC)（88.6mg，0.3mmol），N,N-二甲基丙烯酰胺(DMA)（208.2mg，2.1mmol）和2-葡糖胺乙基甲基丙烯酰胺（GAEMA）（183.6mg，0.6mmol）溶解在25 mL聚合管中的N,N-二甲基甲酰胺和去离子水的混合溶剂中，然后加入偶氮二异丁腈(AIBN)（1.48mg，9.0μmol）并用氮气脱气30分钟。然后将聚合过程在70°C下搅拌24小时。共聚物通过去离子水透析纯化3天，然后冻干。所得共聚物P（MPC-DMA- GAEMA）命名为PMDG。该共聚物以AIBN为引发剂，通过MPC、DMA和GAEMA的自由基聚合得到。
水凝胶的制备和表征
水凝胶由共聚物PMDG、硼砂和银纳米颗粒（Ag NPs）溶液简单混合而成。将共聚物PMDG以12% w / v浓度溶解在去离子水中并超声处理10 min，然后以4：1（v / v）的比例加入硼砂溶液（1.5%，w / v），并加入1.0% Ag NPs，命名为PMDG-12%/ Borax / Ag NPs水凝胶。
实施例
将实施例1中制备水凝胶时，将共聚物PMDL以10%w/v和14%w/v浓度溶解在去离子水中，其他条件不变，与实施例1相同，即可获得PMDL-10%/Borax/Ag NPs1.0 和PMDL-14%/Borax/Ag NPs1.0水凝胶敷料。
实施例
将实施例1中制备水凝胶时，Ag NPs纳米颗粒浓度分别为0.5%、1.5%、2.0%，其他条件不变，与实施例1相同，即可获得PMDL-10%/Borax/Ag NPs0.5、PMDL-10%/Borax/AgNPs1.5和PMDL-10%/Borax/Ag NPs2.0水凝胶敷料。
实施例
共聚物的合成
将磺基甜菜碱甲基丙烯酸酯 (SBMA)（83.8mg，0.3mmol），N,N-二甲基丙烯酰胺(DMA)（208.2mg，2.1mmol）和2-葡糖胺乙基甲基丙烯酰胺（GAEMA）（183.6mg，0.6mmol）溶解在25 mL聚合管中的N,N-二甲基甲酰胺和去离子水的混合溶剂中，然后加入4,4'-偶氮双(4-氰基戊酸)（ACVA）（2.52mg，9.0μmol）并用氮气脱气30分钟。然后将聚合过程在70°C下搅拌24小时。共聚物通过去离子水透析纯化3天，然后冻干。所得共聚物P（SBMA-DMA- GAEMA）命名为PSDG。该共聚物以ACVA为引发剂，通过SBMA、DMA和GAEMA的自由基聚合得到。
水凝胶的制备和表征
水凝胶由共聚物PSDG、硼砂和硫化铜纳米粒子（CuS NPs）溶液简单混合而成。将共聚物PSDG以12% w / v浓度溶解在去离子水中并超声处理10 min，然后以4：1（v / v）的比例加入硼砂溶液（1.5%，w / v），并加入1.0% CuS NPs，命名为PSDG-12%/ Borax / CuS NPs水凝胶。
实施例
共聚物的合成
将甲基丙烯酸羧酸甜菜碱 (CBMA)（91.7mg，0.4mmol），N,N-二甲基丙烯酰胺(DMA)（208.2mg，2.1mmol）和2-乳酰氨基乙基甲基丙烯酰胺(LAEMA)（234.3mg，0.5mmol）溶解在25 mL聚合管中的N,N-二甲基甲酰胺和去离子水的混合溶剂中，然后加入4,4'-偶氮双(4-氰基戊酸)（ACVA）（2.52mg，9.0μmol）并用氮气脱气30分钟。然后将聚合过程在70°C下搅拌24小时。共聚物通过去离子水透析纯化3天，然后冻干。所得共聚物P（CBMA-DMA- LAEMA）命名为PCDL。该共聚物以ACVA为引发剂，通过CBMA、DMA和LAEMA的自由基聚合得到。
水凝胶的制备和表征
水凝胶由共聚物PCDL、硼砂和金纳米粒子（Au NPs）溶液简单混合而成。将共聚物PCDL以12% w / v浓度溶解在去离子水中并超声处理10 min，然后以4：1（v / v）的比例加入硼砂溶液（1.5%，w / v），并加入1.0% Au NPs，命名为PSDG-12%/ Borax / Au NPs水凝胶。
本发明通过双键封端的糖单体中的1.2-二醇与硼酸中的硼羟基之间的相互作用，结合纳米颗粒抗菌剂的简单混合，得到基于可逆二醇硼酸盐键的网络交联结构抗菌水凝胶敷料；该水凝胶敷料具有快速的自愈能力和优异的注射性，以及良好的粘附性，对大肠杆菌和金黄色葡萄球菌具有有效的抗菌活性。
性能测试：
水凝胶对大肠杆菌(E. coli, ATCC25922)和金黄色葡萄球菌(S. aureus,ATCC6538)的抗菌性能利用平板计数法进行评估。将大肠杆菌和金黄色葡萄球菌单菌落分别接种于LB和TSB液体培养基中，37℃连续摇培养至对数生长期。然后将细菌稀释至1×107CFU mL-1供进一步使用。所有的水凝胶都用PBS清洗以去除未交联的聚合物。取100 μL水凝胶转移至24孔板上，将20 μL菌悬液(大肠杆菌和金黄色葡萄球菌)涂于水凝胶表面孵育4h，加入980 μL灭菌PBS溶液，轻轻重新悬浮存活菌。阴性对照组:在980 mL PBS溶液中加入20µL悬浮液。取100µL菌悬液，均匀平铺于琼脂板上，37℃孵育24 h。记录并拍摄琼脂板上的菌落。
培养24 h后琼脂板菌落形成单元图像如5图所示，以无水凝胶的细菌培养组为空白。与对照组相比，用PMDL-12%/Borax/Ag NPs1.0水凝胶处理的琼脂板的细菌数量明显减少，说明水凝胶对大肠杆菌和金黄色葡萄球菌具有良好的抗菌效果。
水凝胶的粘附性能:利用数码相机对PMDL-12%/Borax/Ag NPs1.0水凝胶与不同基底的粘附能力进行定性评价。如图6所示，水凝胶能有效地粘附在玻璃、聚丙烯、橡胶、金属和纸张表面。
将PMDL-12%/Borax/Ag NPs1.0水凝胶用罗丹明B染色，如图7所示，可以清楚地观察到水凝胶紧紧地粘附在新鲜猪皮上，并在扭曲弯曲后完整地保留在皮肤组织上，没有任何分离。
本申请通过简单的一步交联法设计并制备了一种多功能抗菌水凝胶敷料，用于加速伤口修复，其中包含硼砂，AgNPs和两性离子糖聚合物聚[（2-甲基丙烯酰氧基乙基磷酸胆碱）-co-（N，N-二甲基丙烯酰胺）-co-（2-乳糖酰胺乙基甲基丙烯酰胺）]（PMDL）。水凝胶体系中的动态可逆硼酸酯键是由聚合物链和硼砂中的半乳糖残基构建而成的，使水凝胶在被破坏后具有快速的自愈能力。银NPs作为一种可控释放的抗菌纳米颗粒，参与水凝胶网络，使其具有良好的抗菌活性。并且糖聚合物的DMA链段可以通过氢键与各种材料的表面结合，从而得到优异的粘附性。然后通过流变试验研究了PMDL/硼砂/银NPs水凝胶的力学和自修复性能。所获得的PMDL-12%/Borax/Ag NPs1.0水凝胶具有快速的自愈能力和优异的注射性，以及对各种材料的生物组织和表面的良好粘附性。此外，水凝胶对大肠杆菌和金黄色葡萄球菌具有有效的抗菌活性，可以预防伤口护理中的细菌感染。多功能水凝胶还具有良好的细胞相容性和血液相容性，在生物医学领域具有广阔的应用前景。
以上所述是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明所述原理的前提下，还可以作出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种快速自修复可注射纳米复合抗菌水凝胶敷料的制备方法，其特征在于，包含以下步骤：
（1）将双键封端的糖单体、两性离子、功能单体以及引发剂均匀混合于溶剂中，通入氮气鼓泡10-60分钟，将混合溶液升温至65~80度下进行聚合反应，反应8~30小时，得聚合产物，将粗产物在去离子水中常温下透析1~3天，并进行冷冻干燥得到聚合物；
（2） 将聚合物以5~30wt%的浓度溶解到在去离子水、PBS或生理盐水溶液中，加入含硼酸的硼羟基单体1.0~10wt%，然后通过超声将纳米粒子0.1~10wt%分散到上述混合溶液中，静置10分钟，得到快速自修复可注射纳米复合抗菌水凝胶敷料。
2.依据权利要求1所述的快速自修复可注射纳米复合抗菌水凝胶敷料的制备方法，其特征在于，所述双键封端的糖单体结构是以下中的任意一种：
3.依据权利要求2所述的快速自修复可注射纳米复合抗菌水凝胶敷料的制备方法，其特征在于，所述两性离子是：2-甲基丙烯酰氧乙基磷酸胆碱、磺基甜菜碱甲基丙烯酸酯、甲基丙烯酸羧酸甜菜碱 中的任意一种。
4.依据权利要求3所述的快速自修复可注射纳米复合抗菌水凝胶敷料的制备方法，其特征在于，所述功能单体是：N,N-二甲基丙烯酰胺、甲基丙烯酸羟乙酯、丙烯酸羟乙酯、甲基丙烯酸羟丙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸、丙烯酸、甲基丙烯酸缩水甘油酯、丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酰胺、丙烯酰胺、甲基丙烯酸2-氨基乙基酯盐酸盐、N-(3,4-二羟基苯乙基)甲基丙烯酰胺或3-(甲基丙烯酰氧)丙基三甲氧基硅烷中的任意一种。
5.依据权利要求4所述的快速自修复可注射纳米复合抗菌水凝胶敷料的制备方法，其特征在于，所述引发剂是：4,4'-偶氮双(4-氰基戊酸)、偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁酸二甲酯、过硫酸铵、过硫酸钾或过氧化苯甲酰中的任意一种。
6.依据权利要求5所述的快速自修复可注射纳米复合抗菌水凝胶敷料的制备方法，其特征在于，所述反应溶剂是去离子水、甲醇、乙醇、N,N-二甲基甲酰胺、乙二醇单甲醚、乙二醇单乙醚中的一种或几种的混合。
7.依据权利要求6所述的快速自修复可注射纳米复合抗菌水凝胶敷料的制备方法，其特征在于，所述纳米粒子是：银纳米粒子、金纳米粒子、二氧化钛粒子、氧化锌纳米粒子、铜纳米粒子、氧化铈纳米粒子、二氧化钛纳米粒子、硫化铜纳米粒子其中的一种或多种。
8.依据权利要求7所述的快速自修复可注射纳米复合抗菌水凝胶敷料的制备方法，其特征在于，所述含硼酸的硼羟基单体是：硼砂、苯硼酸、1,4-苯二硼酸、4-甲酯基苯硼酸、2-羟甲基苯硼酸、2-羟基苯硼酸、4-胺基苯硼酸、3-氨基苯硼酸、2-氨基苯硼酸、3-羟基苯硼酸、4-羟基苯硼酸、4-羟甲基苯硼酸、1,4-苯二硼酸、2-萘硼酸、4,4'-联苯基二硼酸、2-羟甲基苯基硼酸、2-羟甲基-5-氨基苯基硼酸、5-甲基丙烯酰胺基-1,2-苯并恶硼酮中的一种或多种。
9.依据权利要求8所述的快速自修复可注射纳米复合抗菌水凝胶敷料的制备方法，其特征在于，单体按重量和100%计算，双键封端的糖单体的含量为10 ~ 30 wt%，两性离子的含量为10 ~ 50 wt%，功能单体的含量为40-60 wt%。
10.依据权利要求1-9任意一项所述的快速自修复可注射纳米复合抗菌水凝胶敷料的制备方法得到的快速自修复可注射纳米复合抗菌水凝胶敷料。
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