CN112500505A - 一种高分子银复合物及其制备方法和应用 - Google Patents
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Abstract
本发明公开了一种高分子银复合物及其制备方法和应用，常温下分别配制一定浓度的硝酸银水溶液和一定浓度的含羧基的高分子水溶液；在搅拌条件下，将硝酸银水溶液缓慢滴加到含羧基的高分子水溶液中，所述硝酸银水溶液中硝酸银与含羧基的高分子中羧基的摩尔比为1:1‑1:15；滴加完毕后，即得到高分子银复合物。本发明提供的高分子银复合物对大肠杆菌、白色念珠菌和金黄色葡糖球菌均有显著的抑制作用，可缓慢释放银离子，减小了银的细胞毒作用，且制备简单，是一种绿色环保的新型抗菌剂。
Description
技术领域
本发明属于抑菌技术领域，具体涉及一种高分子银复合物及其制备方法和应用。
背景技术
基于银的各种材料在消毒剂中具有丰富的应用。如银离子以及纳米级和微米级的单价银，都具有较好的抑菌性能。但是以上材料均存在一定问题，如银离子虽然具有较强的抑菌能力，但银离子一次性地作用于皮肤，比较容易产生细胞毒性。而纳米银，虽然能够缓慢释放银离子，一定程度降低了银离子的毒性，但纳米银通常呈棕黑色，在使用过程中容易形成皮肤或衣物污染，给使用带来不便。因此，基于银的消毒剂(包括抑菌剂)的研究，在保证其消毒/抑菌效应的基础上，还需解决两大问题：1)缓慢释放银离子，减小银的细胞毒作用；2)改善消毒剂(抑菌剂)的颜色，使其美观同时不易造成皮肤和衣物污染。
发明内容
本发明的目的之一是提供一种高分子银复合物的制备方法，步骤操作简单，且成本低。
本发明的目的之二是提供由上述制备方法制得的高分子银复合物，抑菌效果显著，且细胞毒性低，颜色浅或无颜色。
本发明的目的之三是提供上述高分子银复合物作为抗菌材料的应用。
为实现上述目的，本发明采用的技术方案如下：一种高分子银复合物的制备方法，包括以下步骤：
(1)常温下分别配制一定浓度的硝酸银水溶液和一定浓度的含羧基的高分子水溶液；所述含羧基的高分子的分子量范围为1kDa-2500kDa之间，所述含羧基的高分子水溶液浓度为0.1-3wt％；
(2)在搅拌条件下，将硝酸银水溶液缓慢滴加到含羧基的高分子水溶液中，所述硝酸银水溶液中硝酸银与含羧基的高分子中羧基的摩尔比为1:1-1:15；滴加完毕后，即得到高分子银复合物。
优选的，所述含羧基的高分子为透明质酸、海藻酸、明胶、阿拉伯胶、羧基化壳聚糖以及羧甲基纤维素的羧酸或盐中的一种或几种。
更优选的，所述含羧基的高分子为透明质酸钠。
优选的，所述透明质酸钠的分子量为1000kDa。
优选的，所述硝酸银水溶液中硝酸银与透明质水溶液中透明质酸羧基的摩尔比为1:1.5。
本发明另一方面还提供了由所述的方法制备得到的高分子银复合物。
此外，本发明还提供了所述的高分子银复合物作为抗菌材料的应用。
经抑菌环试验检测，本发明提供的高分子银复合物对大肠杆菌、白色念珠菌和金黄色葡糖球菌均有显著的抑制作用，在37℃的培养条件下形成了≥13mm的抑菌环，具有显著的抑菌作用；且细胞毒性低，可以用作抗菌材料使用。
与现有技术相比，本发明具有如下有益效果：
1.本发明的高分子银复合物经抑菌环试验检测对大肠杆菌、白色念珠菌和金黄色葡糖球菌均有显著的抑制作用，在37℃的培养条件下形成了≥13mm的抑菌环，具有显著的抑菌作用。
2.本发明的高分子银复合物可缓慢释放银离子，同硝酸银相比，显著降低了硝酸银的细胞毒性，表明该复合物同银离子相比具有更高的生物安全性。
3.本发明的高分子银复合物分散于水中呈无色透明的胶体状(或由于高分子本身颜色呈极浅的淡黄色)，同纳米银相比，该复合物不会造成皮肤或衣物的染色污染，同时还具有一定保湿锁水作用。
4.该复合物制备工艺简单，价格低廉，是一种绿色环保的新型抗菌剂。
附图说明
图1为本发明实施例3制得的透明质酸银分散于水照片；
图2为本发明实施例3制得的透明质酸银的粒径分布图；
图3为本发明实施例3制得的透明质酸银的银离子释放速度图；
图4为本发明实施例3制得的透明质酸银的CCK-8细胞毒性试验；
图5为本发明实施例3制得的透明质酸银的银离子释放机理图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步详细说明。
实施例1
称取10mg AgNO3于EP管中，加入5mL双蒸水，震荡使其溶解；称取25mg海藻酸钠(分子量为2500kDa)于EP管中(银离子与海藻酸钠中羧基摩尔比为1:1)，加入15mL双蒸水，震荡使其溶解；将溶解的AgNO3缓慢滴加到海藻酸钠溶液中，制得500ppm的海藻酸银，其分散于水中呈无色透明状，在光束照射下呈现淡蓝色乳光，表明该体系为胶体体系。
实施例2
称取10mg AgNO3于EP管中，加入5mL双蒸水，震荡使其溶解；称取130mg羧基化壳聚糖(分子量为1kDa)于EP管中(银离子与羧基化壳聚糖中羧基摩尔比约为1:10)，加入15mL双蒸水，震荡使其溶解；将溶解的AgNO3缓慢滴加到海藻酸钠溶液中，制得500ppm的壳聚糖银，其分散于水中呈淡黄色透明状，在光束照射下呈现淡蓝色乳光，表明该体系为胶体体系。
实施例3
称取10mg AgNO3于EP管中，加入5mL双蒸水，震荡使其溶解；称取34mg高分子量透明质酸钠(分子量为1000kDa)于EP管中(银离子与透明质酸钠中羧基摩尔比为1:1.5)，加入15mL双蒸水，震荡使其溶解；将溶解的AgNO3缓慢滴加到透明质酸钠溶液中，制得500ppm的透明质酸银，其分散于水中呈无色透明状，在光束照射下呈现淡蓝色乳光，表明该体系为胶体体系(图1)。采用粒度分析仪测得粒径分布见图2，其平均粒径为38nm。
实施例4
将实施例3制备得到的透明质酸银5mL置于透析袋中(截留分子量8kDa)，将透析袋置于50mLPBS缓冲液(pH7.4)中，37℃搅拌24h，于不同时间取样测定透析介质中银离子含量。结果如图3所示，可以看到同硝酸银相比，透明质酸银具有显著的银离子缓释作用。
实施例5：抑菌环试验
5.1试验器材
(1)金黄色葡萄球菌(ATCC 6538)、大肠杆菌(8099)、白色念珠菌(ATCC 10231)菌悬液。
(2)抑菌剂载体(5mm直径园形新华一号定性滤纸片，经压力蒸汽灭菌处理后，置120℃烤干2h，保存备用)。
(3)活菌培养计数所需器材。
(4)微量移液器(5μl～50μl，可调式)。
(5)游标卡尺。
(6)营养琼脂培养基、胰蛋白胨大豆琼脂培养基与沙堡琼脂培养基
5.2操作程序
(1)抑菌片的制备：对液体抑菌剂，取无菌并干燥的滤纸片。每片滴加实际使用浓度(60ppm)抑菌剂溶液20μl，然后将滤纸片平放于清洁的无菌平皿内，开盖置温箱(37℃)中烤干，或置室温下自然干燥后备用。
(2)阴性对照样片的制备：取无菌干燥滤纸片，每片滴加无菌蒸馏水20μl，干燥后备用。
(3)试验菌的接种：用无菌棉拭子蘸取浓度为5×105cfu/ml～5×106cfu/ml试验菌悬液，在营养琼脂培养基平板表面均匀涂抹3次。每涂抹1次，平板应转动60°，最后将棉拭子绕平板边缘涂抹一周。盖好平皿，置室温干燥5min。
(4)抑菌剂样片贴放：每次试验贴放1个染菌平板，每个平板贴放4片试验样片，1片阴性对照样片，共5片。用无菌镊子取样片贴放于平板表面。各样片中心之间相距25mm以上，与平板的周缘相距15mm以上。贴放好后，用无菌镊子轻压样片，使其紧贴于平板表面。盖好平皿，置37℃温箱，培养16h～18h观察结果。用游标卡尺测量抑菌环的直径(包括贴片)并记录。试验重复3次。
测量抑菌环时，应选均匀而完全无菌生长的抑菌环进行。测量其直径应以抑菌环外沿为界。
5.3评价规定
(1)抑菌作用的判断：抑菌环直径大于7mm者，判为有抑菌作用。抑菌环直径小于或等于7mm者，判为无抑菌作用。
(2)3次重复试验均有抑菌作用结果者，判为合格。
(3)阴性对照组应无抑菌环产生。否则试验无效。
检测得实施例1至3分别制备的海藻酸银、壳聚糖银以及透明质酸银，在60ppm条件下，对大肠杆菌、白色念珠菌以及金黄色葡萄球菌的抑菌圈均大于7mm(见表1)，表明三者均具有较好的抑菌能力。
表1海藻酸银、壳聚糖银以及透明质酸银的抑菌圈
实施例6：稳定性试验
1)4℃冰箱留样：将样品放置于4℃冰箱，10d后进行抑菌或杀菌性能测试(抑菌环试验)。
2)加速试验：将样品置于60℃恒温箱内，保持相对湿度≥75％，10d后进行抑菌或杀菌性能测试(抑菌环试验)。
3)光照试验：将样品置于光照(4500±500lx)下，10d后进行抑菌或杀菌性能测试(抑菌环试验)。
检测得实施例3制备得到的透明质酸银分别在4℃、加速、光照条件放样10天下，对大肠杆菌、白色念珠菌以及金黄色葡萄球菌的抑菌圈均大于7mm(见表2)，表明本发明制得的透明质酸银具有较好的稳定性。
表2透明质酸银的稳定性试验结果
实施例7：细胞毒性实验
取对数生长期的小鼠海马神经元HT-22细胞以3-5×104cells/ml的密度接种于96孔板，每孔100μL细胞悬液，每组设置6个复孔，孵育至细胞生长密度到70％左右。孵育结束后，用1mL注射器吸取96孔板内的培养基，各孔加入各浓度所需药物(硝酸银、柠檬酸银和透明质酸银)，继续孵育24h。孵育结束后，避光加入10μL CCK-8溶液，培养箱避光孵育1h，孵育结束后，酶标仪测定560nm波长处的吸光度(Optical density，OD)值，用空白孔(培养基+CCK-8)校准吸光度值，各组细胞存活率计算公式为：细胞相对存活率＝(实验孔OD值-空白孔OD值)/(对照孔OD值-空白孔OD值)×100％。
如图4所示，硝酸银、柠檬酸银和透明质酸银组在低浓度(0.5ppm以下)时对HT-22细胞毒性很低，在高浓度(0.5ppm以上)时，细胞毒性明显增强；但是，在高浓度(0.5ppm以上)时，与硝酸银给药组和柠檬酸银给药组相比，透明质酸银的细胞毒性明显较低。以上结果表明，透明质酸银可缓慢释放银离子，减小银的细胞毒作用。
从图5也可以看出，本发明制备得到的高分子透明质酸银可以缓慢解离出Ag+，从而发挥杀菌作用。
Claims (7)
1.一种高分子银复合物的制备方法，其特征在于，包括以下步骤：
(1)常温下分别配制一定浓度的硝酸银水溶液和一定浓度的含羧基的高分子水溶液；所述含羧基的高分子的分子量范围为1kDa-2500kDa之间，所述含羧基的高分子水溶液浓度为0.1-3wt％；
(2)在搅拌条件下，将硝酸银水溶液缓慢滴加到含羧基的高分子水溶液中，所述硝酸银水溶液中硝酸银与含羧基的高分子中羧基的摩尔比为1:1-1:15；滴加完毕后，即得到高分子银复合物。
2.根据权利要求1所述的一种高分子银复合物的制备方法，其特征在于，所述含羧基的高分子为透明质酸、海藻酸、明胶、阿拉伯胶、羧基化壳聚糖以及羧甲基纤维素的羧酸或盐中的一种或几种。
3.根据权利要求2所述的一种高分子银复合物的制备方法，其特征在于，所述含羧基的高分子为透明质酸钠。
4.根据权利要求3所述的一种高分子银复合物的制备方法，其特征在于，所述透明质酸钠的分子量为1000kDa。
5.根据权利要求1所述的一种高分子银复合物的制备方法，其特征在于，所述硝酸银水溶液中硝酸银与透明质水溶液中透明质酸羧基的摩尔比为1:1.5。
6.由权利要求1至5任一项所述的制备方法制备得到的高分子银复合物。
7.权利要求6所述的高分子银复合物作为抗菌材料的应用。
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