CN112062904B - 一种京尼平交联抗菌肽/季铵化纤维素复合水凝胶抑菌剂及其制备方法与应用 - Google Patents
一种京尼平交联抗菌肽/季铵化纤维素复合水凝胶抑菌剂及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种京尼平交联抗菌肽/季铵化纤维素复合水凝胶抑菌剂及其制备方法与应用。本发明方法包括将纤维素粉分散到尿素碱体系中，预冻处理，快速搅拌得到纤维素溶液；加入环氧氯丙烷，搅拌混匀，反应，产物洗涤至中性，得到纤维素水凝胶；加入过硫酸钾和水，反应；再加入二甲基二烯丙基氯化铵，进行接枝反应，得到季铵化纤维素水凝胶；加入到乳酸链球菌素水溶液中，调节pH为5.0，加入京尼平进行交联反应，产物洗涤、干燥。该方法制备水凝胶抑菌剂操作简单、制备迅速、可塑性较高。所得抑菌剂安全无毒、可降解、生物相容性高，同时具有高效抑菌性和广谱性、持久性和易回收利用等特点，不会产生细菌耐药性，具有良好的应用前景。
Description
技术领域
本发明属于抑菌材料技术领域，具体涉及一种京尼平交联抗菌肽/季铵化纤维素复合水凝胶抑菌剂及其制备方法与应用。
背景技术
食品、药品、农产品或医疗用品等材料多容易受到大肠杆菌、金黄色葡萄球菌等微生物污染。为减少微生物污染造成的损失，研究者们相继开发出如壳聚糖和抗菌肽、生物碱等天然抑菌剂、部分金属离子和金属氧化物等无机抑菌剂、酚类和季铵盐类有机抑菌剂等多种抑菌材料。大多抑菌剂若直接使用，则会出现难以回收、耐热性差、持久性差和广谱抑菌性差等缺点。所以更多采用将一种或多种抑菌类物质接枝负载于特定载体之上，增强其实用性。通常载体采用纤维素、壳聚糖、淀粉等生物质材料或其他有机合成材料，基于绿色安全和环境友好等因素，纤维素和壳聚糖等生物质材料或其衍生材料因具有较好的生物相容性、安全无毒、生物可降解等优点而受到重视。
纤维素作为一种天然高分子聚合物，众多的羟基为其衍生化应用提供基础。可再生、可降解、安全无毒和环境友好等特征，使得纤维素产品在食品材料、医药材料、组织工程和农业工程等领域具有广泛的应用。为更好地满足不同应用，纤维素通常会在不同溶剂体系中制备成粉末、球珠、薄膜、纤维或凝胶状。水凝胶是一种通过分子间作用力、化学键、氢键，或金属离子络合而成的具有多孔网络结构的高分子聚合物，具有保水保湿、吸附缓释等，广泛应用于农业生产、食品加工、医疗器材等。
单独的纤维素产品不具备抑菌性能，不能抑制或阻止微生物对其的破坏，为改善纤维素材料的抗菌性能，通常会对其进行物理、化学或生物修饰，如吸附复合、包埋、接枝共聚等，赋予抑制微生物活性的能力。乳酸链球菌素(Nisin)是由乳酸菌产出的一种细菌素，是唯一可被允许添加至食品中的细菌素，对革兰氏阳性菌具有强烈的抑制作用。但是在食品中酶的降解和与其他蛋白质、脂肪等成分的相互作用下，Nisin在食品贮存过程中可能会丧失其活性。所以寻求一种对Nisin的保护措施显得尤为重要。京尼平是一种从栀子中提取的天然安全交联剂，可以成功将Nisin接枝于纤维素表面，使得纤维素产品具有一定的抗菌作用。但是，由于Nisin对革兰氏阴性菌的抑制能力较弱，为获得具有广谱抗菌性的纤维素材料，可进一步进行结构修饰增强纤维素产品的抗菌性能。季铵盐型阳离子物质如二甲基二烯丙基氯化铵，对革兰氏阴性菌亦具有一定的抑制作用，可以增强抗菌肽/纤维素复合材料的广谱抑菌性能。
现有文献报道的抑菌剂多为抗生素、纳米银等复合材料，而这些材料一般易使细菌产生抗药性、价格昂贵或抑菌效果低、持久性差、不耐热等问题。蛋白、多肽类抑菌剂容易受到食品内酶的水解或对温度等环境的适应能力差等缺点。对于纤维素基的抗菌剂，大多只考虑了将壳聚糖、海藻酸盐、季铵盐等单独作为改性剂，且对交联剂的选择也比较单一，在广谱抑菌性能和稳定性方面相对复合改性较差。
因此，亟需开发出一种持久性、广谱性、耐热性好、安全性高、不易产生耐药性的绿色抑菌剂。
发明内容
针对现有技术存在的缺点和不足，本发明的主要目的在于提供一种京尼平交联抗菌肽/季铵化纤维素复合水凝胶抑菌剂的制备方法。在尿素碱体系制备纤维素凝胶基础上，通过过硫酸钾引发纤维素水凝胶产生自由基接枝二甲基二烯丙基氯化铵，然后通过京尼平将乳酸链球菌素交联至季铵化纤维素水凝胶，制备一种高效长效广谱抑菌剂，以提高纤维素基抑菌材料结构稳定性和循环使用性能。
本发明的另一目的在于提供一种通过上述方法制备得到的京尼平交联抗菌肽/季铵化纤维素复合水凝胶抑菌剂。
本发明的再一目的在于提供一种上述京尼平交联抗菌肽/季铵化纤维素复合水凝胶抑菌剂的应用。
本发明目的通过以下技术方案实现：
一种京尼平交联抗菌肽/季铵化纤维素复合水凝胶抑菌剂的制备方法，包括如下步骤：
(1)将清洗干燥后的纤维素粉分散到尿素碱体系中，预冻处理，快速搅拌得到纤维素溶液；
(2)向步骤(1)所得纤维素溶液中加入环氧氯丙烷，搅拌混匀，反应，所得产物洗涤至中性，得到纤维素水凝胶；
(3)取步骤(2)所得纤维素水凝胶，加入过硫酸钾和水，反应；再加入二甲基二烯丙基氯化铵，进行接枝反应，得到季铵化纤维素水凝胶；
(4)取步骤(3)所得季铵化纤维素水凝胶，加入到乳酸链球菌素水溶液中，调节pH为5.0，加入京尼平进行交联反应，所得产物洗涤、干燥，即获得所述的京尼平交联抗菌肽/季铵化纤维素复合水凝胶抑菌剂。
步骤(1)中所述的尿素碱体系中氢氧化钠、尿素、水的配比优选为质量比5～10:10～15:75～85；更优选为质量比7:12:81。
步骤(1)中所述的纤维素粉的添加量优选为尿素碱体系质量的2wt％～4wt％。
步骤(1)中所述的预冻处理的条件优选为：温度-5～-20℃，时间1～10h。
步骤(2)中所述的环氧氯丙烷的添加量优选为纤维素溶液质量的5wt％～10wt％。
步骤(2)中所述的反应的条件优选为：温度30～60℃，时间10～18h。
步骤(2)中所述的洗涤是指经蒸馏水、乙醇多次洗涤。
步骤(3)中所述的过硫酸钾的添加量优选按25～100mg/g纤维素水凝胶计。
步骤(3)中所述的水的添加量优选按40～50mL/g纤维素水凝胶计。
步骤(3)中所述的反应的条件优选为：温度为60～80℃的水浴摇床中反应20～30min。
步骤(3)中所述的二甲基二烯丙基氯化铵的添加量优选按1～6g/g纤维素水凝胶计。
步骤(3)中所述的接枝反应的时间优选为2～3h。
步骤(4)中所述的季铵化纤维素水凝胶的添加量优选为乳酸链球菌素水溶液质量的1wt％～2wt％。
步骤(4)中所述的乳酸链球菌素水溶液的浓度优选为0.5wt％～4wt％。
步骤(4)中所述的京尼平的添加量优选为乳酸链球菌素水溶液质量的0.02wt％～0.15wt％。
步骤(4)中所述的交联反应的条件优选为：温度30～60℃，时间15～24h。
步骤(4)中所述的洗涤是指用蒸馏水洗涤。
步骤(4)中所述的干燥是指40～50℃，尤其是45℃下干燥。
一种京尼平交联抗菌肽/季铵化纤维素复合水凝胶抑菌剂，通过上述制备方法制备得到。
上述京尼平交联抗菌肽/季铵化纤维素复合水凝胶抑菌剂在农业、食品、医药等领域中的应用。用于抑制革兰氏阴性和革兰氏阳性等细菌。
上述京尼平交联抗菌肽/季铵化纤维素复合水凝胶抑菌剂在制备抗大肠杆菌和/或金黄色葡萄球菌药物中的应用。
在所述的应用中，所述的京尼平交联抗菌肽/季铵化纤维素复合水凝胶抑菌剂的有效浓度优选为8～12g/L；更优选为10g/L。
本发明具有如下优点及有益效果：
(1)本发明采用原位化学交联制备纤维素水凝胶，步骤简单，凝胶化速度高，可塑性高，可满足不同产品实际形状需求；
(2)本发明所得京尼平交联抗菌肽/季铵化纤维素复合水凝胶抑菌剂应用于农业、食品、医药等领域中抑制革兰氏阴性和革兰氏阳性等细菌，具有广谱抑菌性；
(3)采用本发明的抑菌剂制备简单，具有抑菌高效性、持久性、无毒和良好的生物相容性。
附图说明
图1是本发明复合抑菌剂的制备方法的工艺流程图。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。
下述实施例中未注明具体实验条件的试验方法，通常按照常规实验条件或按照制造厂所建议的实验条件。所使用的材料、试剂等，如无特殊说明，为从商业途径得到的试剂和材料。
实施例1
本实施例的一种京尼平交联抗菌肽/季铵化纤维素复合水凝胶抑菌剂的制备方法，其工艺流程如图1所示，具体步骤如下：
(1)纤维素的冷冻溶解：将充分清洗干燥后的4g纤维素粉(购于上海麦克林生化科技有限公司，产品型号CAS：9004-34-6)充分分散在100g氢氧化钠/尿素/水(7:12:81wt％)体系中，预冻温度-20℃，预冻1h，在500rpm搅拌速度下充分搅拌5min；
(2)制备纤维素水凝胶：向纤维素溶液中加入10％的环氧氯丙烷，500rpm转速搅拌混匀30min，50℃条件下加热12h凝胶化，所得产物经蒸馏水、乙醇多次洗涤至中性，除去氢氧化钠、尿素和环氧氯丙烷；
(3)制备季铵化纤维素水凝胶：将纤维素水凝胶进行切片处理，取1g干燥后的水凝胶于250mL锥形瓶中，加入45mg过硫酸钾、50mL水，于70℃水浴摇床中反应20min，产生自由基；再向溶液中加入4g二甲基二烯丙基氯化铵，继续加热接枝反应2h，得到季铵化纤维素水凝胶；
(4)制备京尼平交联抗菌肽/季铵化纤维素复合水凝胶抑菌剂：取1g干燥后的季铵化纤维素水凝胶加入到100mL 2％的Nisin水溶液中，调节pH为5.0，京尼平添加量为0.09％，交联温度为45℃，交联24h后，所得产物经蒸馏水多次清洗，于45℃干燥，室温储存备用。
(5)水凝胶抑菌剂抑菌性能测试：挑取大肠杆菌(ATCC25922)和金黄色葡萄球菌(ATCC25923)典型菌落摇床培养16h，用磷酸缓冲液将菌液稀释至10-5CFU，分别取0.4g干燥后的水凝胶抑菌剂和未改性水凝胶(具体制备方法参考步骤(1)和(2))空白对照组在光照强度为90uw/cm2的紫外光照下杀菌30min，加入到40mL菌液稀释液中摇床培养18h后，涂布计数，三组平行实验，计算平均抑菌率。
实施例2
本实施例与实施例1的不同之处在于：
将步骤(1)中的纤维素粉的添加量调整为3g，预冻温度调整为-15℃，预冻时间调整为5h，转速调整为300rpm，搅拌时间调整为15min；
将步骤(2)中环氧氯丙烷添加量调整为8％，转速调整为300rpm，凝胶化时间调整为15h，凝胶化温度调整为30℃；
将步骤(3)中的过硫酸钾添加量调整为100mg，自由基引发温度调整为60℃，二甲基二烯丙基氯化铵添加量调整为3g，接枝时间调整为2.5h；
将步骤(4)中的Nisin水溶液浓度调整为2％，京尼平添加量调整为0.05％，调节交联温度为40℃，交联时间为20h，所得产物经蒸馏水多次清洗，于45℃干燥，室温储存备用。
实施例3
本实施例与实施例1的不同之处在于：
将步骤(1)中的纤维素粉的添加量调整为2g，预冻温度调整为-10℃，预冻时间调整为7h，转速调整为600rpm，搅拌时间调整为10min；
将步骤(2)中环氧氯丙烷添加量调整为5％，转速调整为600rpm，凝胶化时间调整为18h，凝胶化温度调整为40℃；
将步骤(3)中的过硫酸钾添加量调整为25mg，自由基引发温度调整为80℃，二甲基二烯丙基氯化铵添加量调整为6g，接枝时间调整为2.5h；
将步骤(4)中的Nisin水溶液浓度调整为0.5％，京尼平添加量调整为0.02％，调节交联温度为30℃,交联时间为16h，所得产物经蒸馏水多次清洗，于45℃干燥，室温储存备用。
实施例4
本实施例与实施例1的不同之处在于：
将步骤(1)中的纤维素粉的添加量调整为2g，预冻温度调整为-5℃，预冻时间调整为10h，转速调整为800rpm，搅拌时间调整为10min；
将步骤(2)中环氧氯丙烷添加量调整为8％，转速调整为800rpm，凝胶化时间调整为12h，凝胶化温度调整为60℃；
将步骤(3)中的过硫酸钾添加量调整为50mg，自由基引发温度调整为65℃，二甲基二烯丙基氯化铵添加量调整为1g，接枝时间调整为3h；
将步骤(4)中的Nisin水溶液浓度调整为4％，京尼平添加量调整为0.15％，调节交联温度为50℃,交联时间为18h，所得产物经蒸馏水多次清洗，于45℃干燥，室温储存备用。
实施例5
本实施例与实施例1的不同之处在于：
将步骤(1)中的纤维素粉的添加量调整为2g，预冻温度调整为-20℃，预冻时间调整为3h，转速调整为700rpm，搅拌时间调整为8min；
将步骤(2)中环氧氯丙烷添加量调整为8％，转速调整为700rpm，凝胶化时间调整为10h，凝胶化温度调整为30℃；
将步骤(3)中的过硫酸钾添加量调整为50mg，自由基引发温度调整为70℃，二甲基二烯丙基氯化铵添加量调整为6g，接枝时间调整为3h；
将步骤(4)中的Nisin水溶液浓度调整为3％，京尼平添加量调整为0.05％，调节交联温度为60℃,交联时间为15h，所得产物经蒸馏水多次清洗，于45℃干燥，室温储存备用。
实施例1～5的抑菌剂对大肠杆菌和金黄色葡萄球菌的抑制性能检测结果如表1所示：
表1抑菌性能检测结果统计
| 大肠杆菌抑菌率(％) | 金黄色葡萄球菌抑菌率(％) | |
| 实施例1 | 99.97 | 100 |
| 实施例2 | 99.95 | 99.99 |
| 实施例3 | 99.98 | 99.99 |
| 实施例4 | 99.93 | 99.99 |
| 实施例5 | 100 | 100 |
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (5)
1.一种京尼平交联抗菌肽/季铵化纤维素复合水凝胶抑菌剂的制备方法，其特征在于：包括如下步骤：
（1）将清洗干燥后的纤维素粉分散到尿素碱体系中，预冻处理，快速搅拌得到纤维素溶液；
（2）向步骤（1）所得纤维素溶液中加入环氧氯丙烷，搅拌混匀，反应，所得产物洗涤至中性，得到纤维素水凝胶；
（3）取步骤（2）所得纤维素水凝胶，加入过硫酸钾和水，反应；再加入二甲基二烯丙基氯化铵，进行接枝反应，得到季铵化纤维素水凝胶；
（4）取步骤（3）所得季铵化纤维素水凝胶，加入到乳酸链球菌素水溶液中，调节pH为5.0，加入京尼平进行交联反应，所得产物经洗涤、干燥，即获得所述的京尼平交联抗菌肽/季铵化纤维素复合水凝胶抑菌剂；
步骤（1）中所述的纤维素粉的添加量为尿素碱体系质量的2 wt %～4 wt %；
步骤（1）中所述的预冻处理的条件为：温度-5～-20 ℃，时间1～10 h ；
步骤（2）中所述的环氧氯丙烷的添加量为纤维素溶液质量的5 wt %～10 wt %；
步骤（2）中所述的反应的条件为：温度30～60 ℃，时间10～18 h；
步骤（3）中所述的过硫酸钾的添加量按25～100 mg/g纤维素水凝胶计；
步骤（3）中所述的水的添加量按40～50 mL/g纤维素水凝胶计；
步骤（3）中所述的反应的条件为：温度为60～80 ℃的水浴摇床中反应20～30 min；
步骤（3）中所述的二甲基二烯丙基氯化铵的添加量按1～6 g/g纤维素水凝胶计；
步骤（3）中所述的接枝反应的时间为2～3 h；
步骤（4）中所述的季铵化纤维素水凝胶的添加量为乳酸链球菌素水溶液质量的1 wt %～2 wt %；
步骤（4）中所述的京尼平的添加量为乳酸链球菌素水溶液质量的0.02 wt %～0.15 wt% ；
步骤（4）中所述的交联反应的条件为：温度30～60 ℃，时间15～24 h。
2.根据权利要求1所述的京尼平交联抗菌肽/季铵化纤维素复合水凝胶抑菌剂的制备方法，其特征在于：
步骤（1）中所述的尿素碱体系中氢氧化钠、尿素、水的配比为质量比5～10:10～15:75～85；
步骤（4）中所述的乳酸链球菌素水溶液的浓度为0.5 wt %～4 wt %。
3.一种京尼平交联抗菌肽/季铵化纤维素复合水凝胶抑菌剂，其特征在于：通过权利要求1或2所述的制备方法制备得到。
4.权利要求3所述的京尼平交联抗菌肽/季铵化纤维素复合水凝胶抑菌剂在农业、食品、医药领域中的应用。
5.权利要求3所述的京尼平交联抗菌肽/季铵化纤维素复合水凝胶抑菌剂在制备抗大肠杆菌和/或金黄色葡萄球菌药物中的应用。
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