CN113398312B - 一种负载金属有机框架纳米酶与葡萄糖的抗菌纤维及其制备方法与应用 - Google Patents

一种负载金属有机框架纳米酶与葡萄糖的抗菌纤维及其制备方法与应用 Download PDF

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CN113398312B
CN113398312B CN202110582078.9A CN202110582078A CN113398312B CN 113398312 B CN113398312 B CN 113398312B CN 202110582078 A CN202110582078 A CN 202110582078A CN 113398312 B CN113398312 B CN 113398312B
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吴刚
何王美
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South China University of Technology SCUT
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Abstract

本发明公开了一种负载金属有机框架纳米酶与葡萄糖的抗菌纤维及其制备方法与应用。本发明方法包括如下步骤：将葡萄糖、亲水性高分子化合物、疏水性高分子化合物配成纺丝液，通过纺丝得到负载葡萄糖的纤维膜；将葡萄糖氧化酶通过酰胺键反应修饰在具有类似过氧化物酶催化活性的金属有机框架纳米粒子表面，得到葡萄糖氧化酶修饰的金属有机框架纳米酶，然后沉积在负载葡萄糖的纤维膜表面，风干，即可。本发明方法操作简单、成本低。本发明所得抗菌纤维，葡萄糖和金属有机框架纳米酶之间存在级联抗菌特性，无需外源提供可原位起抗菌作用，对多种细菌有高效的抗菌性能，可应用于感染创面的治疗及修复，具有良好的应用前景。

Description

一种负载金属有机框架纳米酶与葡萄糖的抗菌纤维及其制备 方法与应用
技术领域
本发明属于抗菌医用材料领域，具体涉及一种负载金属有机框架纳米酶与葡萄糖的抗菌纤维及其制备方法与应用。
背景技术
纳米酶是一种可表现出类似天然酶特性(如过氧化物酶、过氧化氢酶、氧化酶等)的纳米材料，其制备成本低、易于合成且相对于天然酶具有稳定活性的优点。金属有机框架(MOF)纳米酶由于具有高孔隙率及比表面积而受到人们的广泛关注。特别是具有类似过氧化物酶(POD)特征的金属有机框架纳米酶可在pH＝3～4时与H2O2通过Fenton反应产生羟基自由基(·OH)，利用·OH直接破坏细菌膜结构从而发挥有效的抗菌作用。目前，具有级联反应特性的金属有机框架纳米酶体系可原位产生H2O2并消耗H2O2，避免了H2O2对周边组织的损伤，这引起研究人员的兴趣。已有研究表明在金属有框架纳米酶表面负载葡萄糖氧化酶(GOx)，并在葡萄糖存在的情况下构建一种具有级联催化产生·OH的复合纳米酶，其过程主要是通过GOx分解葡萄糖产生葡萄糖酸和H2O2，降低环境的pH值和供给产生·OH的H2O2。
金属有机框架纳米酶通常以粉末形式直接使用，但皮肤组织所含的葡萄糖含量较低，使得该材料体系的级联反应活性较低，这极大限制了其在感染创面的实际应用。
聚己内酯(Polycaprolactone，PCL)为美国食品与药物管理局(Food and drugadministration，FDA)批准的可用于临床的聚合物材料。因其良好的生物相容性，被广泛地应用于伤口愈合敷料、组织再生支架和药物递送纳米载体。PCL具有强疏水性，常与亲水性材料复合来增强其亲水性质，如明胶、胶原、聚乙烯吡咯烷酮等。
发明内容
为了克服现有技术的缺点和不足，本发明的首要目的在于提供一种负载金属有机框架纳米酶与葡萄糖的抗菌纤维的制备方法。
本发明的另一目的在于提供通过上述制备方法制备得到的抗菌纤维。
本发明的再一目的在于提供上述抗菌纤维在制备抗菌敷料中的应用。
本发明的目的通过下述技术方案实现：
一种负载金属有机框架纳米酶与葡萄糖的抗菌纤维的制备方法，包括如下步骤：
S1、将葡萄糖、亲水性高分子化合物、疏水性高分子化合物配成纺丝液，通过纺丝得到负载葡萄糖的纤维膜；
S2、将葡萄糖氧化酶通过酰胺键反应修饰在具有类过氧化物酶催化活性的金属有机框架纳米粒子表面，得到葡萄糖氧化酶修饰的金属有机框架纳米酶；
S3、将步骤S2所得葡萄糖氧化酶修饰的金属有机框架纳米酶溶液沉积在步骤S1所得负载葡萄糖的纤维膜表面，风干，即获得所述的负载金属有机框架纳米酶与葡萄糖的抗菌纤维。
步骤S1中所述的亲水性高分子化合物包括但不限于明胶、胶原、聚乙烯吡咯烷酮中的至少一种。所述的明胶的胶强度优选为100～300g Bloom。
步骤S1中所述的疏水性高分子化合物包括但不限于聚己内酯、聚乳酸、聚氨酯中的至少一种。所述的聚己内酯的平均分子量优选为10000～80000。
步骤S1中所述的葡萄糖的用量优选按其在体系中的质量分数为3％～10％计，更优选按6.7％计；所述的亲水性高分子化合物的用量优选按其在体系中的质量分数为8％～14％计，更优选按10％计；所述的疏水性高分子化合物的用量优选按其在体系中的质量分数为12％～18％计，更优选按14％计。
步骤S1中所述的负载葡萄糖的纤维膜可为混纺或三明治多层结构。
当所述的负载葡萄糖的纤维膜为混纺时，制备步骤为：将葡萄糖溶解在水中，加入冰乙酸，搅拌均匀，再加入2,2,2-三氟乙醇，搅拌均匀，最后加入亲水性高分子化合物和疏水性高分子化合物，继续搅拌，获得混合纺丝液，进行纺丝，纺丝结束后获得混纺，即为所述的负载葡萄糖的纤维膜；
当所述的负载葡萄糖的纤维膜为三明治多层结构时，制备步骤为：将葡萄糖溶解在水中，加入冰乙酸，搅拌均匀，再加入2,2,2-三氟乙醇，搅拌均匀，然后加入亲水性高分子化合物，继续搅拌，获得纺丝液A；另外用2,2,2-三氟乙醇溶解疏水性高分子化合物，搅拌，获得纺丝液B；依次抽取纺丝液A、纺丝液B、纺丝液A进行纺丝，纺丝结束后获得三明治多层纤维膜，即为所述的负载葡萄糖的纤维膜。
所述的水、冰乙酸、2,2,2-三氟乙醇的体积比优选为1:(1～13):(1～13)，其中，冰乙酸和2,2,2-三氟乙醇的总量与水的体积比为14:1。
步骤S1中所述的纺丝优选为静电纺丝，静电纺丝的条件为：电压10～20kV，纺丝速度0.5～2mL/h，接收距离为15～20cm，纺丝体积为2～8mL。
步骤S2中所述的具有类过氧化物酶催化活性的金属有机框架纳米粒子，可选自NH2-Fe-MIL88B(CAS：1341134-09-5)、NH2-Fe-MIL53(CAS：1291088-77-1)、NH2-Fe-MIL101(CAS：1189182-85-1)、NH2-UiO-66(Zr)(CAS：1260119-00-3)中的至少一种。
步骤S2的具体步骤如下：在葡萄糖氧化酶溶液中加入EDC(1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐)，进行活化反应；然后加入NHS(N-羟基琥珀酰亚胺)、具有类过氧化物酶催化活性的金属有机框架纳米粒子分散液，搅拌状态下反应；反应结束后离心，洗涤，干燥，即得到葡萄糖氧化酶修饰的金属有机框架纳米酶。
所述的葡萄糖氧化酶溶液的浓度优选为1～5mg/mL，更优选为5mg/mL；所述的金属有机框架纳米粒子分散液的浓度优选为1～8mg/mL，更优选为2mg/mL；所述的EDC和NHS的浓度均优选为10～30mmol/L，更优选为20mmol/L；所述的葡萄糖氧化酶溶液、EDC、NHS、金属有机框架分散液的配比优选为体积比10:1:1:50。
所述的活化反应的条件优选为温度35～40℃、时间10～20min，更优选为温度37℃、时间15min。
所述的搅拌状态下反应的条件优选为转速50～150rpm、温度35～40℃、时间1.5～2.5h，更优选为转速100rpm、温度37℃、时间2h。
步骤S3中所述的沉积优选通过浸渍法或滴涂法实现，当通过滴涂法实现时，滴涂次数优选为1～10次，更优选为2～8次。滴涂法简单易操作，可定量沉积金属有机框架纳米酶。
步骤S3中所述的葡萄糖氧化酶修饰的金属有机框架纳米酶水溶液的浓度优选为0.16～1mg/mL，更优选为0.06525mg/mL。
一种负载金属有机框架纳米酶与葡萄糖的抗菌纤维，通过上述制备方法制备得到。
上述负载金属有机框架纳米酶与葡萄糖的抗菌纤维在制备抗菌敷料中的应用。所述的抗菌敷料可应用于感染创面的治疗及修复。
为解决抗菌成分(金属有机框架纳米酶、葡萄糖)的有效级联催化，本发明以聚己内酯/明胶纤维膜作为抗菌成分的载体，制备出负载葡萄糖和金属有机框架纳米酶的抗菌敷料。主要包括如下步骤：基于静电纺丝技术将聚己内酯、明胶、葡萄糖糖共混制备混纺纤维膜，或通过逐层静电纺丝制备三明治多层结构纤维膜；根据简单物理吸附法将葡萄氧化酶修饰的金属有机框架纳米酶沉积在电纺纤维膜表面，获得具有级联抗菌特性的抗菌敷料。
本发明的有益效果是：
(1)本发明的制备方法操作简单、成本低；
(2)亲水性材料可改善组合纤维的疏水性，而疏水性材料为葡萄糖和金属有机框架纳米酶的提供良好的载体环境，可很好的缓释葡萄糖并沉积纳米酶；
(3)葡萄糖和金属有机框架纳米酶之间存在级联抗菌特性，无需外源提供可原位起抗菌作用。
(4)本发明制备的抗菌纤维对多种细菌有高效的抗菌性能。该材料抗菌机制基于金属有机框架纳米酶与葡萄糖原位反应形成的自由基。所述抗菌敷料的主要特点：(1)抗菌成分为金属有机框架纳米酶+葡萄糖的组合；(2)亲水/疏水材料组成的纤维膜；(3)葡萄糖预先包埋在纤维内部；(4)金属有机框架纳米酶沉积在电纺纤维膜表面。
附图说明
图1为本发明实施例中不同质量分数的聚己内酯电纺纤维膜的扫描电镜图；其中，(a)为8％PCL纺丝液制得的聚己内酯电纺纤维膜，(b)为10％PCL纺丝液制得的聚己内酯电纺纤维膜，(c)为12％PCL纺丝液制得的聚己内酯电纺纤维膜，(d)为14％PCL纺丝液制得的聚己内酯电纺纤维膜。
图2为本发明实施例中聚己内酯及其复合电纺纤维膜的接触角变化情况图。
图3为本发明实施例中聚己内酯/明胶/葡萄糖亲疏水三明治纤维膜的结构示意图。
图4为本发明实施例中聚己内酯/明胶/葡萄糖静电纺丝液实物图。
图5为本发明实施例中聚己内酯/明胶/葡萄糖混合纤维膜的结构示意图。
图6为本发明实施例中聚己内酯/明胶/葡萄糖电纺纤维膜的扫描电镜图；其中，(a)为聚己内酯/明胶/葡萄糖电纺纤维膜，(c)为(a)的局部放大图，(b)为沉积有金属有机框架纳米酶的聚己内酯/明胶/葡萄糖电纺纤维膜，(d)为(b)的局部放大图。
图7为本发明实施例中聚己内酯/明胶/葡萄糖电纺纤维膜中葡萄糖的释放曲线；其中，(a)为标准曲线，(b)为葡萄糖的释放曲线。
图8为本发明实施例中不同酶负载量的金属有机框架纳米酶检测结果图；其中，(a)为标准曲线，(b)为不同浓度下制备的金属有机框架纳米酶的酶负载量结果。
图9为本发明实施例中金属有机框架纳米酶的扫描电镜图；其中，(a)为金属有机框架纳米粒子，(b)为金属有机框架纳米酶。
图10为本发明应用实施例中金属有机框架纳米酶抗菌敷料对耐甲氧西林的金黄色葡萄球菌和大肠杆菌的抑菌圈形成实物图及抑菌圈直径变化情况；其中，(a)为实物图，(b)为抑菌圈直径变化情况。
图11为本发明应用实施例中金属有机框架纳米酶抗菌敷料与MRSA、E.coli共培养后涂板计数实物图。
图12为本发明应用实施例中金属有机框架纳米酶抗菌敷料对耐甲氧西林的金黄色葡萄球菌和大肠杆菌的细菌生物膜抑制实物图及定量测定结果；其中，(a)(b)为实物图，(c)(d)为定量测定结果。
具体实施方式
下面通过具体实施例对本发明进行详细地描述，但本发明的实施方式不限于此。
实施例1聚己内酯电纺纤维膜的制备
分别称取1.2g、1.5g、1.8g、2.1gPCL(平均分子量为80000)粒料加入含15mL2,2,2-三氟乙醇中，室温搅拌12h，得到8％、10％、12％、14％PCL的透明纺丝液。
由于溶液浓度、电纺速率、电压、接收距离及湿度温度都会影响纤维的形貌，因此在保证静电纺丝液稳定且静电纺丝过程顺利进行的情况下，制备出均匀、连续的纤维成为纺丝的关键问题之一。经过调节影响纺丝的外界因素等因素，得出了最优纺丝条件：纺丝浓度为14％，电压为10kV，接收距离为15cm，推进速率为2.0mL/h。利用10mL一次性注射器抽取4mL的纺丝液置于注射泵上，采用21号平口针头并调节针头与接收板的距离及电压，进行静电纺丝。纺丝结束后，将PCL纤维膜放入37℃干燥一夜，得到纺丝连续无缺陷的纤维，接触角为130°，表现为强疏水性。
本实施例中不同质量分数的聚己内酯电纺纤维膜的扫描电镜图如图1所示；聚己内酯电纺纤维膜的接触角测试结果如图2所示。
实施例2聚己内酯/明胶/葡萄糖三明治多层结构电纺纤维膜的制备
称取1.0g葡萄糖在高温下溶于1mL去离子水，继续加入9mL冰乙酸，搅拌均匀；加入5mL2,2,2-三氟乙醇，混合均匀；加入1.5g明胶(胶强度约为250gBloom)，继续搅拌2h，获得均一的10％GE/6.7％D-glu纺丝液。另外用15mL2,2,2-三氟乙醇溶解2.1g PCL(平均分子量为80000)，室温过夜搅拌均匀，获得均一的14％PCL纺丝液。
首先利用10mL一次性注射器抽取1mL的GE/D-glu纺丝液置于注射泵上，采用21号平口针头并调节针头与接收板的距离及电压，进行静电纺丝。纺丝条件：电压为20kV，接收距离为15cm，推进速率为2.0mL/h。其次利用10mL一次性注射器抽取2mL的PCL纺丝液于注射泵上，采用21号平口针头并调节针头与接收板的距离及电压，进行静电纺丝。纺丝条件：电压为10kV，接收距离为15cm，推进速率为2.0mL/h。最后再利用10mL一次性注射器抽取1mL的GE/D-glu纺丝液置于注射泵上，采用21号平口针头并调节针头与接收板的距离及电压，进行静电纺丝。纺丝条件：电压为20kV，接收距离为15cm，推进速率为2.0mL/h。纺丝结束后获得亲疏水性含葡萄糖的三明治结构纤维膜。
本实施例中制备的聚己内酯/明胶/葡萄糖三明治结构纤维膜(PCL/GE/D-glu)的结构示意图如图3所示。
实施例3聚己内酯/明胶/葡萄糖混纺纤维膜(PCL/GE/D-glu)的制备
称取1.0g葡萄糖在高温下溶于1mL去离子水；继续加入9mL冰乙酸，搅拌均匀；加入5mL2,2,2-三氟乙醇，混合均匀；最后加入2.1g聚己内酯和1.5g明胶(胶强度约为250gBloom)，继续搅拌2h，获得均一的黄色透明溶液，如图4所示。最终纺丝液中溶剂比(水/冰乙酸/2,2,2-三氟乙醇)为1:9:5，溶质分数(聚己内酯/明胶/葡萄糖)为14％PCL/10％GE/6.7％D-glu。
利用10mL一次性注射器抽取4mL的纺丝液置于注射泵上，采用21号平口针头并调节针头与接收板的距离及电压，进行静电纺丝。纺丝条件：电压为18kV，接收距离为15cm，推进速率为2.0mL/h。纺丝结束后，将聚己内酯/明胶/葡萄糖电纺纤维膜放入37℃干燥一夜，得到纺丝连续无缺陷的纤维，接触角为50°，表现为良好的亲水性。
本实施例制备的聚己内酯/明胶/葡萄糖混纺纤维膜(PCL/GE/D-glu)的结构示意图如图5所示；聚己内酯/明胶/葡萄糖混纺纤维膜的扫描电镜图如图6(a)所示；聚己内酯/明胶/葡萄糖混纺纤维膜的接触角如图2所示。
实施例4静电纺丝纤维膜葡萄糖释放曲线的检测
(1)制备葡萄糖检测液：称取1200U的辣根过氧化物酶、1200U的葡萄糖氧化酶，10mL 5mM的3,3',5,5'-四甲基联苯胺溶液，溶于pH＝7的PBS缓冲液，定容至100mL。
(2)制作葡萄糖标准曲线：分别取10μL不同浓度(0.2、0.4、0.6、0.8、1mM)的葡萄糖溶液，加入1mL的显色液，在37℃孵育15min，分别移取100μL到96孔板，在酶标仪检测OD652nm值，取平均值。
本实施例中聚己内酯/明胶/葡萄糖电纺纤维膜中葡萄糖的释放曲线如图7所示。结果显示，葡萄糖由于极易溶于水，可在10min内快速释放，在抗菌应用中可激活葡萄糖氧化酶修饰的金属有机框架的级联催化特性，原位产生·OH，实现杀菌目的。
实施例5金属有机框架纳米酶的制备
取2mL 5mg/mL GOx溶液与0.2mL 20mM EDC在37℃活化15min，加入0.2mL 20mMNHS、10mL不同浓度的NH2-Fe-MIL88B(CAS：1341134-09-5)(1、2、3、4、5、6、7、8mg/mL)，在100rpm下继续缓慢搅拌2h。反应结束后离心洗涤去上清液，真空干燥过夜，得到不同酶负载量的金属有机框架纳米酶，分别记为G1F1、G1F2、G1F3、G1F4、G1F5、G1F6、G1F7、G1F8，酶负载量分别为182.8、289.1、234.8、213.9、173.3、149.0、125.3、104.2μg/mg，酶负载量最高为289.1μg/mg。
本实施例中不同酶负载量的金属有机框架纳米酶检测结果如图8(b)所示；金属有机框架纳米酶的扫描电镜图如图9(b)所示。
实施例6金属有机框架纳米酶沉积在聚己内酯/明胶/葡萄糖电纺纤维膜表面
配置浓度为0.06525mg/mL的葡萄糖氧化酶修饰的金属有机框架纳米酶(G1F2)溶液，用移液枪吸取50μL的溶液滴加在直径为10mm的GE/D-glu/PCL纤维膜表面，快速渗透，并控制滴加次数为n＝2、4、8，在室温风干一夜。
本实施例中金属有机框架纳米酶抗菌敷料的扫描电镜图如图6(b)所示；金属有机框架纳米酶抗菌敷料的的接触角测试结果如图2所示。
应用实施例1抑菌圈检测
(1)制备菌悬液：用10μL接种环取平板中的单个菌落加入到己灭菌的5mL营养肉汤中，置于37℃的恒温摇床中200rpm震荡12h。用酶标仪测OD600值，再稀释至OD600＝0.1，此时细菌数量为1×108CFU/mL，进一步用无菌生理盐水稀释到106CFU/mL。
(2)琼脂扩散法检测抑菌圈：将样品制备成大小为直径10mm的圆形，正反两面紫外灭菌30min，备用。取MRSA和E.coil用生理盐水将细菌数量稀释到1×106CFU/ml(CFU为菌落形成单位)，取100μL稀释后的菌悬液在营养琼脂固体培养基上平推。将样品置于平板上，在37℃有氧条件下培养12小时，测量并记录抑菌圈直径。重复三次。
本应用实施例中金属有机框架纳米酶抗菌敷料对耐甲氧西林的金黄色葡萄球菌(MRSA)和大肠杆菌(E.coli)的抑菌圈形成实物图及抑菌圈直径变化情况如图10所示。结果显示，G1F2/PCL/GE/D-glu(n＝4、8)具有明显抑菌圈形成的作用，说明G1F2纳米酶与负载葡萄糖的纤维膜之间存在级联抗菌特性。
应用实施例2平板菌落计数检测
将直径为10mm的抗菌敷料置于24孔板中，加入1mL含细菌的营养肉汤(1×106CFU/mL)，确保细菌液完全覆盖样品，在37℃条件下共培养5h。将共培养后的菌悬液吹打均匀，取100μL稀释一定倍数后，取10μL稀释后的菌悬液在营养琼脂培养基表面均匀涂布，置于37℃培养箱中过夜培养后，记录每个平板中形成的菌落数量。
本应用实施例中金属有机框架纳米酶抗菌敷料对耐甲氧西林的金黄色葡萄球菌和大肠杆菌的共培养后涂板实物图及定量测定结果如图11所示。结果显示，金属有机框架纳米酶抗菌敷料对耐甲氧西林的金黄色葡萄球菌和大肠杆菌共培养后涂板，未发现有细菌菌落的产生，说明金属有机框架纳米酶抗菌敷料对耐甲氧西林的金黄色葡萄球菌和大肠杆菌具有高效的抗菌性能。
应用实施例3细菌生物抑制测定
将直径为10mm的抗菌敷料置于24孔板中，加入细菌液(1×106CFU/mL，1mL)，确保细菌液完全覆盖样品，在37℃条件下孵育48小时，每隔24h换下培养基。吸出孔内的培养基，形成的生物膜用生理盐水洗涤一次，然后，使用300μL 1％CV(结晶紫溶液)对生物膜染色，将被染色的生物膜用2mLPBS轻轻洗涤2次，以去除未结合的CV。为了定量分析形成的生物膜，加入500μL95％乙醇，孵育1h，稀释后并进行酶标仪检测595nm处的吸光度。
本应用实施例中金属有机框架纳米酶抗菌敷料对耐甲氧西林的金黄色葡萄球菌和大肠杆菌的细菌生物膜抑制实物图及定量测定结果如图12所示。结果显示，金属有机框架纳米酶抗菌敷料对耐甲氧西林的金黄色葡萄球菌和大肠杆菌作用时，未观察到明显的细菌生物膜，进一步说明金属有机框架纳米酶抗菌敷料对耐甲氧西林的金黄色葡萄球菌和大肠杆菌具有较强的抗菌性能从而抑制了细菌生物膜的形成。
以上所述，仅为本发明较佳的具体实施方式，但本发明保护的范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内所做的任何修改，等同替换和改进等，均应包含在发明的保护范围之内。

Claims (6)

1.一种负载金属有机框架纳米酶与葡萄糖的抗菌纤维的制备方法，其特征在于：包括如下步骤：
S1、将葡萄糖、亲水性高分子化合物、疏水性高分子化合物配成纺丝液，通过纺丝得到负载葡萄糖的纤维膜；
S2、将葡萄糖氧化酶通过酰胺键反应修饰在具有类过氧化物酶催化活性的金属有机框架纳米粒子表面，得到葡萄糖氧化酶修饰的金属有机框架纳米酶；
S3、将步骤S2所得葡萄糖氧化酶修饰的金属有机框架纳米酶溶液沉积在步骤S1所得负载葡萄糖的纤维膜表面，风干，即获得所述的负载金属有机框架纳米酶与葡萄糖的抗菌纤维；
步骤S1中所述的负载葡萄糖的纤维膜为混纺或三明治多层结构；
当所述的负载葡萄糖的纤维膜为混纺时，制备步骤为：将葡萄糖溶解在水中，加入冰乙酸，搅拌均匀，再加入2,2,2-三氟乙醇，搅拌均匀，最后加入亲水性高分子化合物和疏水性高分子化合物，继续搅拌，获得混合纺丝液，进行纺丝，纺丝结束后获得混纺纤维膜，即为所述的负载葡萄糖的纤维膜；
当所述的负载葡萄糖的纤维膜为三明治多层结构时，制备步骤为：将葡萄糖溶解在水中，加入冰乙酸，搅拌均匀，再加入2,2,2-三氟乙醇，搅拌均匀，然后加入亲水性高分子化合物，继续搅拌，获得纺丝液A；另外用2,2,2-三氟乙醇溶解疏水性高分子化合物，搅拌，获得纺丝液B；依次抽取纺丝液A、纺丝液B、纺丝液A进行纺丝，纺丝结束后获得三明治多层结构纤维膜，即为所述的负载葡萄糖的纤维膜；
所述的水、冰乙酸、2,2,2-三氟乙醇的体积配比为1:（1～13）:（1～13），其中，冰乙酸和2,2,2-三氟乙醇的总量与水的体积比为14:1；
步骤S1中所述的纺丝为静电纺丝，静电纺丝的条件为：电压10～20kV，纺丝速度0.5～2mL/h，接收距离为15～20 cm，纺丝体积为2～8 mL；
步骤S2的具体步骤如下：在葡萄糖氧化酶溶液中加入EDC，进行活化反应；然后加入NHS、具有类过氧化物酶催化活性的金属有机框架纳米粒子分散液，搅拌状态下反应；反应结束后离心，洗涤，干燥，即得到葡萄糖氧化酶修饰的金属有机框架纳米酶；
所述的葡萄糖氧化酶溶液的浓度为1～5 mg/mL；所述的金属有机框架纳米粒子分散液的浓度为1～8 mg/mL；所述的EDC和NHS的浓度均为10～30 mmol/L；所述的葡萄糖氧化酶溶液、EDC、NHS、金属有机框架分散液的配比为体积比10:1:1:50；
所述的活化反应的条件为温度35～40℃、时间10～20 min；
所述的搅拌状态下反应的条件为转速50～150 rpm、温度35～40℃、时间1.5～2.5 h。
2.根据权利要求1所述的负载金属有机框架纳米酶与葡萄糖的抗菌纤维的制备方法，其特征在于：
步骤S1中所述的亲水性高分子化合物为明胶、胶原、聚乙烯吡咯烷酮中的至少一种；
步骤S1中所述的疏水性高分子化合物为聚己内酯、聚乳酸、聚氨酯中的至少一种；
步骤S1中所述的葡萄糖的用量按其在体系中的质量分数为3%～10%计；所述的亲水性高分子化合物的用量按其在体系中的质量分数为8%～14%计；所述的疏水性高分子化合物的用量按其在体系中的质量分数为12%～18%计。
3.根据权利要求1所述的负载金属有机框架纳米酶与葡萄糖的抗菌纤维的制备方法，其特征在于：
步骤S3中所述的沉积通过浸渍法或滴涂法实现；当通过滴涂法实现时，滴涂次数为1～10次；
步骤S3中所述的葡萄糖氧化酶修饰的金属有机框架纳米酶水溶液的浓度为0.16～1mg/mL。
4.根据权利要求1所述的负载金属有机框架纳米酶与葡萄糖的抗菌纤维的制备方法，其特征在于：
步骤S2中所述的具有类过氧化物酶催化活性的金属有机框架纳米粒子选自NH2-Fe-MIL88B、NH2-Fe-MIL53、NH2-Fe-MIL101、NH2-UiO-66(Zr)中的至少一种。
5.一种负载金属有机框架纳米酶与葡萄糖的抗菌纤维，其特征在于：通过权利要求1～4任一项所述的制备方法制备得到。
6.权利要求5所述的负载金属有机框架纳米酶与葡萄糖的抗菌纤维在制备抗菌敷料中的应用。
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