CN108453268B - 一种核壳型微米银及其制备方法与应用 - Google Patents
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Abstract
本发明公开了一种核壳型微米银及其制备方法与应用，先将鼠李糖脂溶解到纯水中，配成0.01‑5 g/L的溶液，调至pH 6‑7，混合均匀；再将AgNO3加入至鼠李糖脂溶液中，终浓度为0.1‑1 g/L，混合均匀。放置于60℃‑80℃水浴锅中反应1‑10 h，边搅拌边反应。将步骤反应液冷却至室温，离心，收集沉淀物溶于超纯水中，即得产物。所述核壳型微米银具有广谱杀菌性能，在10 mg/L的浓度下，即对大肠杆菌、铜绿假单胞菌和金黄色葡萄球菌具有杀菌作用。
Description
技术领域
本发明涉及一种利用生物表面活性剂鼠李糖脂合成核壳型微米银的方法，属于微米材料领域。
背景技术
微米银的平均粒径是在10 μm左右的单质银。相较于纳米银而言，微米银不会渗入皮肤或粘膜，而是停留在皮肤表面，杀灭接触皮肤的有害细菌和微生物，成为化妆品应用中的理想抗菌添加剂。微米银是适用于个人护理，医用，药用和动物健康产品的抗菌原料。凡是表面有细菌或需要保护不受微生物侵害的地方都可以使用。目前，制备微米银的方法众多，但还没有一种快速高效简单的方法合成微米银。如Bio-Gate是由纯物理气态制造工艺产微米银，对设备要求高。如CN 201310009307公开了一种表面修饰的由纳米片层组装的微米银球及其制备方法，通过电化学沉积法制得，但该法针对性强、局限性大。因此，开发设备简单，操作简单，节能等优点的合成方法对其微米银的研究及应用有其益处。
发明内容
本发明的目的是提供一种利用鼠李糖脂作为还原剂制备核壳型微米银的方法，在制备核壳型微米银过程中鼠李糖脂既为还原剂又是保护剂，本发明设备、操作简单，反应条件温和。所制备的核壳型微米银具有广谱的杀菌作用。
本发明的目的是通过以下技术方案实现的：
（1）先将鼠李糖脂溶解到纯水中，配成0.01-5 g/L的溶液，调至pH 6-7，混合均匀；再将AgNO3加入至鼠李糖脂溶液中，终浓度为0.01-1 g/L，混合均匀，放置于60℃-80℃水浴锅中反应1-10 h，边搅拌边反应。
（2）将步骤（1）中的反应液冷却至室温，离心，收集沉淀物溶于超纯水中，即得产物。
鼠李糖脂是一种糖脂类的生物表面活性剂，由亲水性的鼠李糖基和疏水性的烷烃链组成；本发明中鼠李糖脂既为还原剂又为保护剂。
所述的鼠李糖脂与硝酸银的质量比为1：1-5:1。
所述的反应温度进一步优选为80℃。
所述的反应时间进一步优选为2 h。
所述的产物粒径3-5 μm左右，微米银外围是单层鼠李糖脂分子。
所述核壳型微米银具有广谱的杀菌作用，包括革兰氏阴性菌、革兰氏阳性菌。
上述的细菌具有为大肠杆菌、铜绿假单胞菌和金黄色葡萄球菌。
上述核壳型微米银的杀菌作用，大肠杆菌的最低杀菌浓度为10 mg/L、铜绿假单胞菌的最低杀菌浓度为4 mg/L和金黄色葡萄球菌的最低杀菌浓度为2 mg/L。
所述的核壳型微米银，主要应用在表面有细菌或需要保护不受微生物侵害的地方，如涂料，塑料，纺织品等。所述核壳型微米银在制备抗菌产品中的应用。
有益效果：
本发明利用鼠李糖脂作为还原剂，直接得到形状规整，表面光滑的核壳型微米银。该方法条件温和，设备、操作简单。鼠李糖脂既是还原剂又是保护剂，减少了反应体系的组分。合成的核壳型微米银具有广谱的杀菌性能，可应用于表面抗菌。
附图说明
图1：本发明制备方法得到的核壳型微米银的扫描电镜；
图2：不同时间合成核壳型微米银的全波长扫描；
图3：不同温度下合成核壳型微米银的全波长扫描；
图4：不同浓度下合成核壳型微米银的全波长扫描；
图5：大肠杆菌在添加不同浓度的核壳型微米银的生长情况；
图6：铜绿假单胞菌在添加不同浓度的核壳型微米银的生长情况；
图7：金黄色葡萄球菌在添加不同浓度的核壳型微米银的生长情况。
具体实施方式
实施例1
先将鼠李糖脂溶解到纯水中，配成1 g/L的溶液，调至pH 6-7，混合均匀；再将AgNO3加入至鼠李糖脂溶液中，终浓度为1 g/L，混合均匀。放置于80℃水浴锅中反应2 h，边搅拌边反应。按5 min、10 min、20 min、40 min、1 h、2 h取样。反应液冷却至室温，离心，收集沉淀物溶于超纯水中，即得产物，见图2。
由图可知，随着时间的增加，最大吸收峰不变始终为451 nm，说明随着时间的增加，产物在不断的累积中，时间不会影响纳米银的尺寸。反应2 h后最大吸收峰值升高为OD451=17.06。因此选取了2 h为最优反应时间。
实施例2
先将鼠李糖脂溶解到纯水中，配成1 g/L的溶液，调至pH 6-7，混合均匀；再将AgNO3加入至鼠李糖脂溶液中，终浓度为1 g/L，混合均匀。分别放置于20℃、37℃、60℃、80℃水浴锅中反应2 h，边搅拌边反应。反应液冷却至室温，离心，收集沉淀物溶于超纯水中，即得产物，见图3。由图可知，当反应温度为80℃时，反应物的最大吸收峰值最大。可见随着温度升高，反应速率最大，产量最高。因此选取了80℃的最优反应温度。
实施例3
先将鼠李糖脂溶解到纯水中，配成1 g/L、2 g/L、4 g/L的溶液，调至pH 6-7，混合均匀；再将AgNO3加入至鼠李糖脂溶液中，终浓度为1 g/L，混合均匀。放置于80℃水浴锅中反应2 h，边搅拌边反应。反应液冷却至室温，离心，收集沉淀物溶于超纯水中，即得产物，见图4。由图可知，添加不同浓度的鼠李糖脂，产物的最大吸收峰有所不同。当鼠李糖脂添加浓度为1 g/L时，反应物的最大吸收峰值最大。因此选取了鼠李糖脂添加浓度为1 g/L的最优反应浓度。
实施例4
将实施例1中反应制得的产物，作为杀菌剂。分别将保存于-80℃的大肠杆菌E.coli、铜绿假单胞菌、金黄色葡萄球菌进行活化，按1%的接种量接种至含有20 ml LB培养基的道康宁离心管中，在离心管中添加0,1,2,4,10 mg/L不同浓度的核壳型微米银，并以只添加核壳型微米银而不加菌株的培养基作为对照组，均置于37℃，200 rpm，培养48 h。按2,4,6,8,10,12,24,36,48 h取样，测其OD600。结果见图5（大肠杆菌）、图6（铜绿假单胞菌） 、图7（金黄色葡萄球菌）。由图可知，对于E.coli来说，Ag@RL的最低抑菌浓度是4 mg/L，最低杀菌浓度是10 mg/L。对于P.aeruginosa来说， Ag@RL的最低抑菌浓度是2 mg/L，最低杀菌浓度是4 mg/L。对于S.aureus来说， Ag@RL的最低抑菌浓度是1 mg/L，最低杀菌浓度是2mg/L。
上述实施例所述方法设备简单，操作方便，反应条件温和。鼠李糖脂既是还原剂又是保护剂，减少了反应体系的组分。合成的核壳型微米银表面光滑，如图1所示。
最后说明的是，以上实施例仅用以说明本发明的技术方案，而非对本发明保护范围的限制。对本发明的任何等同改进，均应落在本发明的保护范围内。
Claims (8)
1.一种核壳型微米银的制备方法，其特征在于，制备步骤如下：
（1）将鼠李糖脂溶解到纯水中，配成1-5 g/L的溶液，调至pH 6-7，混合均匀；
（2）将AgNO3加入至鼠李糖脂溶液中，混合均匀，放置于60℃-80℃水浴锅中反应1-10 h，边搅拌边反应，其中AgNO3终浓度为1 g/L；
（3）将步骤（2）中的反应液冷却至室温，离心，收集沉淀物溶于超纯水中，即得产物。
2.根据权利要求1的所述的核壳型微米银的制备方法，其特征在于，步骤2）中反应温度为80℃。
3.根据权利要求1的所述的核壳型微米银的制备方法，其特征在于，步骤2）中反应时间为2 h。
4.根据权利要求1的所述的核壳型微米银的制备方法，其特征在于，所述产物粒径为3-5 μm，微米银外围是单层鼠李糖脂分子，具有广谱的杀菌作用。
5.权利要求1-4中任意一项所述制备方法制备得到的核壳型微米银，其特征在于，所述核壳型微米银粒径为3-5 μm，微米银外围是单层鼠李糖脂分子。
6.根据权利要求5所述的核壳型微米银，其特征在于，所述核壳型微米银具备广谱的杀菌作用，所述菌包括但不限于大肠杆菌、铜绿假单胞菌或者金黄色葡萄球菌。
7.根据权利要求6所述的核壳型微米银，其特征在于，所述杀菌作用中，能够杀灭的菌体的浓度分别为：大肠杆菌的最低杀菌浓度为10 mg/L、铜绿假单胞菌的最低杀菌浓度为4mg/L、金黄色葡萄球菌的最低杀菌浓度为2 mg/L。
8.权利要求5所述核壳型微米银在制备抗菌产品中的应用。
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