CN110452121A - 一种具有抗菌作用的生物基材料及用途 - Google Patents

一种具有抗菌作用的生物基材料及用途 Download PDF

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CN110452121A
CN110452121A CN201810431508.5A CN201810431508A CN110452121A CN 110452121 A CN110452121 A CN 110452121A CN 201810431508 A CN201810431508 A CN 201810431508A CN 110452121 A CN110452121 A CN 110452121A
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bio
based materials
antibacterial
formula
polyethylene glycol
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陶肖明
杨兴兴
张子恒
李俊
刘世瑞
马琳琳
费宾
梁杏媚
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HONG KONG RES INST OF TEXTILES (HK)
Hong Kong Research Institute of Textiles and Apparel Ltd
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Priority to CN201810431508.5A priority Critical patent/CN110452121A/zh
Priority to PCT/CN2018/085991 priority patent/WO2019213833A1/zh
Priority to US17/053,702 priority patent/US20210084897A1/en
Publication of CN110452121A publication Critical patent/CN110452121A/zh
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Abstract

本发明提供了一种具有抗菌作用的生物基材料，其包括式(1)所示的聚合物、或式(1)所示的聚合物与聚乙二醇形成的混合物作为抗菌活性成分。本发明还提供了所述生物基材料的用途。本发明的具有抗菌作用的生物基材料具有优异且稳定持久的抗菌活性，对多种细菌、真菌都具备显著的抗菌效果，而且还具有优良的生物可降解性、生物相容性等性能，来源于微生物发酵制得的生物基产品，安全性高，适用于工业化生产和大规模使用。

Description

一种具有抗菌作用的生物基材料及用途
技术领域
本发明涉及抗菌材料领域，具体涉及一种具有抗菌作用的生物基聚合物材料及其在制备抗菌材料中的用途。
背景技术
人们生活的环境中存在大量的细菌、真菌和病毒等微生物，其在一定条件下繁殖，不仅会使材料变色、发霉、降解，还威胁着人类的健康。随着生活水平的提高，人们对生活环境的质量和卫生条件的要求也越来越高。因此，抗菌剂、抗菌材料的研究与开发有着极其重要的意义。
抗菌剂主要分为无机抗菌剂、有机抗菌剂和天然抗菌剂三大类。无机抗菌剂使用的抗菌活性成分主要有银、锌等金属离子及金属盐化合物，具有耐热性好、抗菌持久性、不产生耐药性等优点，但是其化学性质活泼不稳定且价格昂贵。有机抗菌剂是指以有机酸类、季铵盐类、苯并咪唑类等有机物为抗菌活性物质的抗菌剂，具有抗菌广谱性，但其抗菌周期短、化学稳定性较差、易产生微生物耐药性，尤其耐热性差，导致其应用范围受限。天然抗菌剂来源于植物、动物或者微生物，通过提取、纯化得到有效抗菌物质，资源极其丰富，而且天然抗菌剂安全无毒、抗菌效果好。
聚3-羟基丁酸酯(PHB)是由微生物产生的一种聚酯，具有优良的生物可降解性、生物相容性和光学活性，广泛应用于纺织、食品包装、手术缝合线、组织工程支架等领域。并且，PHB耐紫外线，不易引起炎症，由于其由微生物细胞制造，完全不含重金属等有毒物质，是极洁净的聚合物材料。
发明内容
为扩大抗菌材料的种类范围，本发明的目的之一是提供一种具有抗菌作用的生物基材料。
本发明的另一目的是提供所述生物基材料的用途。
本发明提供的具有抗菌作用的生物基材料包括式(1)所示的聚合物作为抗菌活性成分，
其中，R表示C1～C5的烷基，m表示0～3的整数，n表示1～20的整数。
本发明人发现：式(1)所示的聚合物，例如低聚合度的聚3-羟基丁酸酯，具备优异的抗菌活性，由此可提供一种新型的生物基抗菌材料。
本发明提供的具有抗菌作用的生物基材料中，还可包括聚乙二醇，聚乙二醇与所述式(1)所示的聚合物形成的混合物作为抗菌活性成分。
本发明人还发现：式(1)所示的聚合物，例如低聚合度的聚3-羟基丁酸酯，与聚乙二醇混合后形成混合物，二者协同作用，所得混合物也具有优异的抗菌活性，由此可提供另一种新型的生物基抗菌材料。
本发明提供的具有抗菌作用的生物基材料中，所述聚乙二醇可以为流体状的所有聚乙二醇产品，优选可以为数均分子量200～2000的聚乙二醇。
本发明提供的具有抗菌作用的生物基材料中，式(1)所示的聚合物与聚乙二醇的质量比可以为1:10～10:1。
本发明提供的具有抗菌作用的生物基材料中，所述混合物中，式(1)所示的聚合物和聚乙二醇都具备一定粘度，二者的混合过程可适当增加混合时间和提高混合温度，优选的制备过程可以为：于80～300℃下将式(1)所示的聚合物与聚乙二醇混合搅拌10min～6h即得。
本发明提供的具有抗菌作用的生物基材料中，式(1)中的取代基R优选可以为甲基、乙基、丙基或异丙基。本发明提供的具有抗菌作用的生物基材料中，式(1)中的m优选可以表示为0或1。
本发明提供的具有抗菌作用的生物基材料中，式(1)所示的聚合物优选可以为低聚合度的聚3-羟基丁酸酯，其可以来源于化学方法合成，也可以来源于PHB高聚物分解；更优选可以来源于微生物发酵制得的PHB高聚物分解，端基分别为羟基和羧基。低聚合度的聚3-羟基丁酸酯的聚合度可以为1～20，优选可以为4～13。
本发明提供的具有抗菌作用的生物基材料中，除使用式(1)所示的聚合物、或式(1)所示的聚合物与聚乙二醇形成的混合物作为活性成分之外，还可以包含现有抗菌材料使用的活性成分外的任何添加成分、添加材料、辅助物质等等，只要是能将活性成分制成任意形式或种类的抗菌材料，且不影响活性成分的抗菌活性即可，本发明不做限制。
本发明还提供了以上技术方案任一项所述的具有抗菌作用的生物基材料在制备抗菌材料中的用途。
本发明还提供了式(1)所示的聚合物、或式(1)所示的聚合物与聚乙二醇形成的混合物在制备抗菌材料中的用途，
其中，R表示C1～C5的烷基，m表示0～3的整数，n表示1～20的整数。
本发明提供的用途中，所述聚乙二醇可以为流体状的所有聚乙二醇产品，优选可以为数均分子量200～2000的聚乙二醇。
本发明提供的用途中，式(1)所示的聚合物与聚乙二醇的质量比可以为1:10～10:1。
本发明提供的用途中，式(1)中的取代基R优选可以为甲基、乙基、丙基或异丙基。本发明提供的用途中，式(1)中的m可以表示为0或1。
本发明提供的用途中，式(1)所示的聚合物优选可以为低聚合度的聚3-羟基丁酸酯，其可以来源于化学方法合成，也可以来源于PHB高聚物分解；更优选可以来源于微生物发酵制得的PHB高聚物分解，端基分别为羟基和羧基。低聚合度的聚3-羟基丁酸酯的聚合度可以为1～20，优选可以为4～13。
上述用途中，抗菌材料可以为任何形式或种类，只要是能将活性成分运用于抗菌材料中，且不影响活性成分的抗菌活性即可。
本发明涉及的抗菌材料包括但不限于抗菌制剂、抗菌织物、卫生用品、医用材料等，尤其适用于纺织、医疗卫生等领域。例如可结合或改性现有聚合物纺织品，再例如用于抗菌制剂，可以用作药物、消毒剂等制剂，又例如用于医用材料，可用于伤口包覆材料、敷料、手术缝合线、植入材料、药物载体及其他生物医用材料。本发明涉及的抗菌材料可以单独使用，也可与其他抗菌制剂、抗菌材料联合使用，还可以用来改性或改造其他抗菌材料。
本发明提供的具有抗菌作用的生物基材料具有以下优点：
(1)具有优异且稳定持久的抗菌活性，对多种细菌、真菌都具备显著的抗菌效果。
(2)除具备抗菌活性之外，本发明的生物基材料还具有优良的生物可降解性、生物相容性等性能，而且可来源于微生物发酵制得的生物基产品，成本低，安全性高，环境友好。
(3)可制成多种形式或种类的抗菌材料，也可和其他抗菌材料联合使用，或用来改造其他材料，得到性能更优的抗菌制剂、抗菌材料，极大丰富了抗菌材料的种类和领域。
(4)本发明无需复杂的制备工艺，适用于工业化生产和大规模使用。
附图说明
图1是实施例1的低聚合度聚3-羟基丁酸酯的质谱图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将进一步描述本发明的示例性实施例的技术方案。
以下实施例所使用的化学试剂如无特别说明则为市售商品，以下实施例所使用的操作或仪器如无特别说明则为本领域常见的操作或仪器。
实施例1
低聚合度聚3-羟基丁酸酯制备过程如下：将10g微生物法制得的PHB母粒加入200mL氯仿中回流24h，然后将混合液加入1L甲醇中过滤，再将滤液中溶剂通过旋转蒸发除去，得到低聚合度的聚3-羟基丁酸酯。取适量低聚合度聚3-羟基丁酸酯溶解于1:1的DCM/甲醇中，0.45μm微孔滤膜过滤，通过质谱仪得到该低聚合度聚3-羟基丁酸酯的质谱图，如图1所示。
由图1的质谱图可以看出，该低聚合度聚3-羟基丁酸酯的重复单元为以下结构，端基分别为羟基和羧基：
重复单元的分子量为86，n为4-13。
实施例2
取实施例1的低聚合度聚3-羟基丁酸酯与数均分子量为600的PEG按质量比1:1混合均匀，150℃加热搅拌4h，冷却至室温，待用。
实施例3
取实施例1的低聚合度聚3-羟基丁酸酯与数均分子量为600的PEG按质量比1:10混合均匀，150℃加热搅拌4h，冷却至室温，待用。
实验例
用磷酸盐缓冲液将实施例1的低聚合度聚3-羟基丁酸酯和实施例2、3的低聚合度聚3-羟基丁酸酯与PEG混合物稀释至20mg/mL，分别使用震荡法(参照国家标准GB 15979-2002)检测其抗菌活性，PBS组做空白对照。所得抗菌性能结果如表1所示。
表1
由表1结果可知：低聚合度聚3-羟基丁酸酯具有非常优异的金黄色葡萄球菌抗菌活性，对于肺炎杆菌也有很明显的抗菌活性；而低聚合度聚3-羟基丁酸酯与聚乙二醇形成的混合物则对于金黄色葡萄球菌和肺炎杆菌都具有非常优异的抗菌活性，此外，混合物对于白色念珠菌的抗菌率也非常显著，具有广谱抗菌效果。
将实施例1-3所得物料放置数月后再按照上述过程检测抗菌活性，与前述检测结果几乎相同，可见其性质稳定，抗菌活性稳定且持久。
由此不难得出，本发明的生物基聚合物材料在抗菌制剂、抗菌材料领域中，尤其是作为医用抗菌材料具有极高的应用潜力。
虽然为了说明本发明，已经公开了本发明的优选实施方案，但是本领域的技术人员应当理解，在不脱离权利要求书所限定的本发明构思和范围的情况下，可以对本发明做出各种修改、添加和替换。

Claims (11)

1.一种具有抗菌作用的生物基材料，其特征在于，包括式(1)所示的聚合物作为抗菌活性成分，
其中，R表示C1～C5的烷基，m表示0～3的整数，n表示1～20的整数。
2.根据权利要求1所述的具有抗菌作用的生物基材料，其特征在于，所述生物基材料还包括聚乙二醇，其与所述式(1)所示的聚合物形成的混合物作为抗菌活性成分。
3.根据权利要求2所述的具有抗菌作用的生物基材料，其特征在于，所述聚乙二醇的数均分子量为200～2000。
4.根据权利要求2所述的具有抗菌作用的生物基材料，其特征在于，所述混合物中，式(1)所示的聚合物与聚乙二醇的质量比为1:10～10:1。
5.根据权利要求4所述的具有抗菌作用的生物基材料，其特征在于，所述混合物的制备过程为：于80～300℃下将式(1)所示的聚合物与聚乙二醇混合搅拌10min～6h即得。
6.根据权利要求1-5任一项所述的具有抗菌作用的生物基材料，其特征在于，所述R表示甲基、乙基、丙基或异丙基；和/或
所述m表示0或1。
7.权利要求1-6任一项所述的具有抗菌作用的生物基材料在制备抗菌材料中的用途。
8.式(1)所示的聚合物、或式(1)所示的聚合物与聚乙二醇形成的混合物在制备抗菌材料中的用途，
其中，R表示C1～C5的烷基，m表示0～3的整数，n表示1～20的整数。
9.根据权利要求8所述的用途，其特征在于，所述聚乙二醇的数均分子量为200～2000。
10.根据权利要求8或9所述的用途，其特征在于，所述式(1)所示的聚合物与聚乙二醇的质量比为1:10～10:1。
11.根据权利要求7-10任一项所述的用途，其特征在于，所述抗菌材料为抗菌制剂、抗菌织物、卫生用品、医用材料中的一种或多种。
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