CN107716943B - 一种抗菌材料海藻酸钠-抗坏血酸纳米银的绿色快速制备方法 - Google Patents
一种抗菌材料海藻酸钠-抗坏血酸纳米银的绿色快速制备方法 Download PDFInfo
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Abstract
本发明公开了一种抗菌材料海藻酸钠‑抗坏血酸纳米银的绿色快速制备方法,该方法包括以下步骤(1)配制海藻酸钠水溶液;(2)将海藻酸钠水溶液加热磁力搅拌过夜;(3)向搅拌过夜后的海藻酸钠水溶液中逐滴滴加的硝酸银溶液,伴随涡旋处理;(4)向步骤(3)得到的混合物中逐滴滴加抗坏血酸溶液,伴随涡旋处理;(5)超声处理混合体系;(6)将超声处理后的混合体系进行离心,弃去上清液,洗涤,将沉淀放置于‑80℃冰箱中冷冻,于真空冷冻干燥机‑40℃冷冻干燥,得到海藻酸钠纳米银颗粒。本发明通过超声制备海藻酸钠‑抗坏血酸纳米银抗菌材料,实现快速、绿色制备,可以作为一种十分具有潜力的保鲜包装材料,用于延长待包装产品的实际货架期。
Description
技术领域
本发明涉及保鲜领域,具体涉及一种抗菌材料海藻酸钠-抗坏血酸纳米银的绿色快速制备方法。
背景技术
由于优良的生物兼容性,新型金属纳米材料日益受到关注。作为一种新材料,纳米银被认为是最普遍使用的金属纳米材料,这主要归因于其独特的物化特性及抗菌性能,因而广泛应用于生物医学、制药及食品包装等领域。纳米银的抗菌性能与其较大的表面空间、热稳定性及对银离子的释放密切相关,而这些均取决于银的类型、大小及形状,另外,纳米银的合成方式也至关重要。相比于金属盐及金属单质,纳米银可以实现对银离子的可控性释放,从而达到持久抗菌的效果。目前,纳米银的合成方法很多,主要分为物理合成、化学合成及生物合成。其中,化学合成最为普遍,主要利用还原剂和稳定剂实现纳米银的合成。然而,具有高反应性的还原剂,比如:肼、N,N-二甲基甲酰胺等,会对环境及生物体产生潜在毒性;常用的稳定剂,比如三苯基膦、聚乙烯吡咯烷酮等,难以分散的问题也不容忽视。另外,化学合成过程中产生的有毒物质也会造成环境压力。与之相反,遵循“绿色化学”原则的纳米银合成方法具有无毒、环境友好等的优势,可有效减少传统合成方法产生的毒害,因而越来越受到研究人员的重视。绿色合成主要涉及非有害溶剂介质,天然还原剂和无毒稳定剂的选择。据报道,天然多糖如壳聚糖和可溶性淀粉对纳米银具有稳定作用,保证其对革兰氏阳性菌和革兰氏阴性菌的持久优异的抗菌活性。
超声是一种依赖强烈的物理剪切和局部温度效应以及声空化形成自由基从而合成功能性纳米材料的有效技术。超声波条件的选择如功率强度,持续时间和反应器配置,影响气蚀泡的强度和数量,从而控制决定纳米银的产量、最终尺寸,表面粗糙度和结构高度。一般而言,超声不仅能够获得所需的平均粒径,而且通常可以产生粒径分布在20nm至100nm范围内的相对更窄的纳米颗粒。此外,超声可以减少反应体系中重金属和有毒溶剂的使用。因此,超声处理通常被认为是遵循“绿色化学”的纳米银合成方法。
为了实现纳米银的合成,特别是绿色、快速合成,需要一种环境友好型的快速制备方法以降低纳米银合成对环境及生物体造成潜在性危害,同时提高制备效率。
发明内容
海藻酸钠是从棕色海藻提取的天然亲水性阴离子多糖,已广泛应用于食品,生物工程和制药领域。它是包含以不同相对比例的MM,MG和GG排列而成的不规则嵌段二元共聚物,含有1-4个线性连接的β-D-甘露糖醛酸(M)和α-L-古洛糖醛酸(G)残基。由于其生物相容性,分散性,易获得性,无毒性和低成本,以及丰富的多功能基团,海藻酸钠可用作制备均相纳米银的胶体稳定剂,也可防止纳米银的凝聚。超声已被开发为一种快速,绿色的纳米银合成技术,海藻酸钠作为稳定剂,抗坏血酸(Vc)作为还原剂。通过紫外-可见(UV-Vis)光谱,透射电子显微镜(TEM),傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)和X射线能级光谱(XPS)分析合成纳米银的形状,尺寸和结构。此外,通过最小抑制浓度(MIC)和抑菌圈(ZOI)方法评估合成纳米银对***(Staphylococcus aureus)和革兰氏阴性菌(Escherichiacoli)的抗菌性能。具有抗菌活性的海藻酸钠纳米银可以保护包装食品免受微生物污染,保持食品品质,延长货架期,可以作为新兴的食品包装材料。
针对现有制备方法存在的不足,本发明提供一种抗菌材料海藻酸钠-抗坏血酸纳米银的绿色快速制备方法,具体包括如下步骤:
(1)配制10-20mg/mL的海藻酸钠水溶液,调节pH至6-13;
(2)将海藻酸钠水溶液加热磁力搅拌过夜,加热温度为40-50℃,磁力搅拌速度为600-1000r/min;
(3)向搅拌过夜后的海藻酸钠水溶液中逐滴滴加的硝酸银溶液,伴随涡旋处理,海藻酸钠水溶液与硝酸银溶液的体积比为100:1-10:1,硝酸银溶液的摩尔浓度为40-60mmol/L;
(4)向步骤(3)得到的混合物中逐滴滴加抗坏血酸溶液,伴随涡旋处理,海藻酸钠水溶液与抗坏血酸溶液的体积比为100:1-10:1,抗坏血酸溶液的浓度为5-15mg/L;
(5)超声处理混合体系,超声条件为:100-900W,15-90℃,0.5-1.5h;
(6)将超声处理后的混合体系以5000-10000rpm离心10-30min,弃去上清液,用蒸馏水反复洗涤3-5次,将沉淀放置于-80℃冰箱中冷冻1-2d,于真空冷冻干燥机-40℃冷冻干燥1-3d,得到海藻酸钠纳米银颗粒。
作为优选,步骤(1)配置得到的海藻酸钠水溶液的pH为12,浓度为15mg/mL。
作为优选,步骤(2)中加热温度为45℃,磁力搅拌速度为1000r/min。
作为优选,步骤(3)中海藻酸钠水溶液与硝酸银溶液的体积比为100:4,硝酸银溶液的摩尔浓度为50mmol/L。
作为优选,步骤(4)中海藻酸钠水溶液与抗坏血酸溶液的体积比为100:2,抗坏血酸溶液的浓度为10mg/L。
作为优选,步骤(5)中,所述超声条件为:300W,30℃,1h。
作为优选,步骤(6)中将超声处理后的混合体系以5000rpm离心10min,弃去上清液,用蒸馏水反复洗涤3次,将沉淀放置于-80℃冰箱中冷冻1d,于真空冷冻干燥机-40℃冷冻干燥2d,得到海藻酸钠纳米银颗粒。
本发明与现有制备方法相比具有下列优点:遵循“绿色化学”原则的海藻酸钠纳米银制备方法表现出无毒、环境友好等优势,减少传统制备方法产生的毒害。通过选择无害溶剂介质,天然还原剂和无毒稳定剂,降低对环境及生物体产生的潜在毒性,并解决难以分散的问题。同时,避免合成过程中产生的有毒物质所造成的环境压力。另外,超声利用强烈的物理剪切和局部温度效应以及声空化形成自由基从而合成纳米材料,具有环境友好、快速、简易等优点。因此,为了实现纳米银的合成,特别是绿色、快速合成,需要一种环境友好型的快速制备方法以降低纳米银合成对环境及生物体造成潜在性危害的劣势,并提高制备效率。
附图说明
图1a-图1f为实施例1制备得到的海藻酸钠-抗坏血酸纳米银颗粒的TEM图;
图2为实施例1中海藻酸钠(a)和海藻酸钠-抗坏血酸纳米银颗粒(b)的FTIR图;
图3为实施例1中海藻酸钠(a)和海藻酸钠-抗坏血酸纳米银颗粒(b)的XRD图;
图4a和图4b分别为实施例1制备得到的海藻酸钠-抗坏血酸纳米银颗粒的XPS分谱图和全谱图;
图5a-图5d为不同反应条件合成纳米银的紫外-可见(UV-Vis)分光光谱图。
具体实施方式
下面结合具体实施例,进一步阐明本发明。
实施例1:配制10mL、15mg/mL的海藻酸钠水溶液(pH12),将海藻酸钠水溶液加热磁力搅拌过夜,加热温度为45℃,磁力搅拌速度为1000r/min,向海藻酸钠水溶液中逐滴滴加0.4mL的硝酸银(AgNO3,50mmol/L)溶液,伴随涡旋处理,向上述混合物中逐滴滴加0.2mL的抗坏血酸(Vc,10mg/L)溶液,伴随涡旋处理,超声处理混合体系,超声条件为:300W,30℃,1h,制备完毕后,避光保存,纳米银溶液用于紫外-可见(UV-Vis)分光光谱及抗菌性能测定,将海藻酸钠纳米银溶液以5000rpm离心10min,弃去上清液,用蒸馏水反复洗涤3次,将沉淀放置于-80℃冰箱中冷冻1d,于真空冷冻干燥机-40℃冷冻干燥2d,得到海藻酸钠纳米银颗粒,通过透射电子显微镜(TEM)、傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)和X射线能级光谱(XPS)分析合成纳米银的形状、尺寸和结构。检测结果如下:
(1)透射电子显微镜(TEM)用于观察样品中小于0.2um的亚显微结构或超微结构。TEM可以探究海藻酸钠-抗坏血酸纳米银颗粒的形状、大小及均一性。如图1a-图1f所示,选定样品的不同区域进行观察,该纳米颗粒均呈现均球状结构,纳米尺寸不超过50nm,且大小均一。这归因于抗坏血酸对银离子的高效还原作用、超声对纳米银前体的破碎作用以及壳聚糖对银纳米颗粒良好的稳定作用。抗坏血酸分子内和分子间氢键网络、银离子与壳聚糖骨架上功能性基团之间的相互作用以及壳聚糖对纳米银的捕获作用均很好的避免由于高表面能导致的纳米银互相聚集。
(2)傅里叶变换红外光谱(FTIR)反映分子内不同化学基团的红外吸收,用于鉴定纳米银中可能存在的生物分子。如图2所示,在壳聚糖的FTIR光谱中,3424cm-1处衍射峰对应羟基(O-H)的拉伸振动,1417cm-1处衍射峰对应羟基(O-H)的变形振动,2932cm-1处衍射峰对应碳氢键(C-H)的伸缩振动,1615cm-1处强和弱衍射峰分别对应羧基(COO-)的不对称和对称拉伸振动,而1097cm-1处衍射峰对应糖苷单元产生的醚键(O-C-O)拉伸振动。比较而言,在壳聚糖-纳米银的FTIR光谱中,羟基(O-H)的衍射峰分别转移至3353.79cm-1和1424.61cm-1,碳氢键(C-H)的衍射峰转移至2917.69cm-1,而羧基(COO-)的衍射峰转移至1634.70cm-1。从FTIR光谱中,我们发现羟基(O-H)和羧基(COO-)是纳米银合成和稳定的主要基团。
(3)X射线与晶体相遇时会发生衍射现象,当一束单色X射线入射到晶体时,由于晶体是由原子规则排列成的晶胞组成,这些规则排列的原子间距离与入射X射线波长具有X射线衍射分析相同数量级,故由不同原子散射的X射线相互干涉,在某些特殊方向上产生强X射线衍射。衍射线在空间分布的方位和强度,与晶体结构密切相关,每种晶体所产生的衍射类型都反映出该晶体内部的原子分配规律,因而X射线衍射已经成为研究晶体物质和某些非晶态物质微观结构的有效方法,很好的用于金属和合金的晶体结构的研究,如纳米银。衍射峰的位置、高度和宽度取决于纳米银的晶体性质,具有高强度的尖衍射峰反映具有高结晶度的小尺寸纳米银微晶的形成。如图3所示,38.26°,44.36°,64.54°,77.5°和81.62°处衍射峰分别对应(1 1 1),(2 0 0),(2 2 0),(3 1 1)和(2 2 2)型纳米银晶面,这证实形成的纳米银呈现面心立方结构,其中(1 1 1)是纳米银的主要晶型取向。
(4)X射线能级光谱(XPS)是原子中最靠内层的电子跃迁时发射出来的,可以反映纳米银的组成和氧化态,证明样品中银(Ag),碳(C)及氧(O)元素的存在。图4a呈现出Ag3d5/2和Ag3d3/2分别在367.88eV和373.78eV处的结合能,二者之间的结合能差(6eV)是AgO的特征结合能差,由此很好的表征AgO的存在;在373.78eV结合能下观察到的Ag3d峰,如图4b所示,进一步表明AgO的存在,从而证实纳米银的形成。
另外,海藻酸钠-抗坏血酸纳米银溶液对革兰氏阳性菌Staphylococcus aureus(KCTC1928)和革兰氏阴性菌Escherichia coli O157:H7(ATCC25922)的最小抑菌浓度(MIC)为11.60mg/mL;该溶液对前者和后者的抑菌圈大小分别为12.58mm和12.75mm,即海藻酸钠-抗坏血酸纳米银溶液表现出很强的抗菌活性,且抗菌效果明显优于单独海藻酸钠溶液及单独抗坏血酸溶液。
实施例2:配制10mL、15mg/mL的海藻酸钠水溶液(pH6),将海藻酸钠水溶液加热磁力搅拌过夜,加热温度为40℃,磁力搅拌速度为1000r/min,向海藻酸钠水溶液中逐滴滴加0.4mL的硝酸银(AgNO3,40mmol/L)溶液,伴随涡旋处理,向上述混合物中逐滴滴0.2mL的加抗坏血酸(Vc,10mg/L)溶液,伴随涡旋处理,超声处理混合体系,超声条件为:100W,15℃,0.5h,制备完毕后,避光保存,纳米银溶液用于紫外-可见(UV-Vis)分光光谱及抗菌性能测定,将海藻酸钠纳米银溶液以5000-10000rpm离心10min,弃去上清液,用蒸馏水反复洗涤3-5次,将沉淀放置于-80℃冰箱中冷冻1d,于真空冷冻干燥机-40℃冷冻干燥2d,得到海藻酸钠纳米银颗粒。
实施例3:配制10mL、15mg/mL的海藻酸钠水溶液(pH13),将海藻酸钠水溶液加热磁力搅拌过夜,加热温度为45℃,磁力搅拌速度为600r/min,向海藻酸钠水溶液中逐滴滴加0.4mL的硝酸银(AgNO3,60mmol/L)溶液,伴随涡旋处理,向上述混合物中逐滴滴加1.0mL的抗坏血酸(Vc,10mg/L)溶液,伴随涡旋处理,超声处理混合体系,超声条件为:100W,30℃,0.5h,制备完毕后,避光保存,纳米银溶液用于紫外-可见(UV-Vis)分光光谱及抗菌性能测定,将海藻酸钠纳米银溶液以5000-10000rpm离心10min,弃去上清液,用蒸馏水反复洗涤3-5次,将沉淀放置于-80℃冰箱中冷冻1d,于真空冷冻干燥机-40℃冷冻干燥2d,得到海藻酸钠纳米银颗粒。
实施例4:配制10mL、10mg/mL的海藻酸钠水溶液(pH12),将海藻酸钠水溶液加热磁力搅拌过夜,加热温度为50℃,磁力搅拌速度为1000r/min,向海藻酸钠水溶液中逐滴滴加0.4mL的硝酸银(AgNO3,50mmol/L)溶液,伴随涡旋处理,向上述混合物中逐滴滴加0.1mL的抗坏血酸(Vc,5mg/L)溶液,伴随涡旋处理,向混合体系中添加蒸馏水,补足至12mL,超声处理混合体系,超声条件为:100W,90℃,0.5h,制备完毕后,避光保存,纳米银溶液用于紫外-可见(UV-Vis)分光光谱及抗菌性能测定,将海藻酸钠纳米银溶液以5000-10000rpm离心10min,弃去上清液,用蒸馏水反复洗涤3-5次,将沉淀放置于-80℃冰箱中冷冻1d,于真空冷冻干燥机-40℃冷冻干燥2d,得到海藻酸钠纳米银颗粒。
实施例5:配制10mL、20mg/mL的海藻酸钠水溶液(pH12),将海藻酸钠水溶液加热磁力搅拌过夜,加热温度为50℃,磁力搅拌速度为800r/min,向海藻酸钠水溶液中逐滴滴加0.1mL的硝酸银(AgNO3,40mmol/L)溶液,伴随涡旋处理,向上述混合物中逐滴滴加0.2mL的抗坏血酸(Vc,5mg/L)溶液,伴随涡旋处理,超声处理混合体系,超声条件为:300W,15℃,1h,制备完毕后,避光保存,纳米银溶液用于紫外-可见(UV-Vis)分光光谱及抗菌性能测定,将海藻酸钠纳米银溶液以5000-10000rpm离心10min,弃去上清液,用蒸馏水反复洗涤3-5次,将沉淀放置于-80℃冰箱中冷冻1d,于真空冷冻干燥机-40℃冷冻干燥2d,得到海藻酸钠纳米银颗粒。
实施例6:配制10mL、15mg/mL的海藻酸钠水溶液(pH12),将海藻酸钠水溶液加热磁力搅拌过夜,加热温度为45℃,磁力搅拌速度为800r/min,向海藻酸钠水溶液中逐滴滴加0.1mL的硝酸银(AgNO3,40mmol/L)溶液,伴随涡旋处理,向上述混合物中逐滴滴加1.0mL的抗坏血酸(Vc,15mg/L)溶液,伴随涡旋处理,超声处理混合体系,超声条件为:300W,90℃,1h,制备完毕后,避光保存,纳米银溶液用于紫外-可见(UV-Vis)分光光谱及抗菌性能测定,将海藻酸钠纳米银溶液以5000-10000rpm离心30min,弃去上清液,用蒸馏水反复洗涤3-5次,将沉淀放置于-80℃冰箱中冷冻1d,于真空冷冻干燥机-40℃冷冻干燥2d,得到海藻酸钠纳米银颗粒。
实施例7:配制10mL、15mg/mL的海藻酸钠水溶液(pH12),将海藻酸钠水溶液加热磁力搅拌过夜,加热温度为50℃,磁力搅拌速度为1000r/min,向海藻酸钠水溶液中逐滴滴加0.1mL的硝酸银(AgNO3,50mmol/L)溶液,伴随涡旋处理,向上述混合物中逐滴滴加0.1mL的抗坏血酸(Vc,10mg/L)溶液,伴随涡旋处理,超声处理混合体系,超声条件为:900W,15℃,1h,制备完毕后,避光保存,纳米银溶液用于紫外-可见(UV-Vis)分光光谱及抗菌性能测定,将海藻酸钠纳米银溶液以5000-10000rpm离心20min,弃去上清液,用蒸馏水反复洗涤3-5次,将沉淀放置于-80℃冰箱中冷冻1d,于真空冷冻干燥机-40℃冷冻干燥2d,得到海藻酸钠纳米银颗粒。
实施例8:配制10mL、15mg/mL的海藻酸钠水溶液(pH12),将海藻酸钠水溶液加热磁力搅拌过夜,加热温度为40℃,磁力搅拌速度为1000r/min,向海藻酸钠水溶液中逐滴滴加1.0mL的硝酸银(AgNO3,50mmol/L)溶液,伴随涡旋处理,向上述混合物中逐滴滴加0.1mL的抗坏血酸(Vc,15mg/L)溶液,伴随涡旋处理,,超声处理混合体系,超声条件为:900W,30℃,1.5h,制备完毕后,避光保存,纳米银溶液用于紫外-可见(UV-Vis)分光光谱及抗菌性能测定,将海藻酸钠纳米银溶液以5000-10000rpm离心10min,弃去上清液,用蒸馏水反复洗涤3-5次,将沉淀放置于-80℃冰箱中冷冻1d,于真空冷冻干燥机-40℃冷冻干燥2d,得到海藻酸钠纳米银颗粒。
实施例9:配制10mL、15mg/mL的海藻酸钠水溶液(pH12),将海藻酸钠水溶液加热磁力搅拌过夜,加热温度为40℃,磁力搅拌速度为600r/min,向海藻酸钠水溶液中逐滴滴加1.0mL的硝酸银(AgNO3,50mmol/L)溶液,伴随涡旋处理,向上述混合物中逐滴滴加0.2mL的抗坏血酸(Vc,5mg/L)溶液,伴随涡旋处理,超声处理混合体系,超声条件为:100W,30℃,1.5h,制备完毕后,避光保存,纳米银溶液用于紫外-可见(UV-Vis)分光光谱及抗菌性能测定,将海藻酸钠纳米银溶液以5000-10000rpm离心30min,弃去上清液,用蒸馏水反复洗涤3-5次,将沉淀放置于-80℃冰箱中冷冻1d,于真空冷冻干燥机-40℃冷冻干燥2d,得到海藻酸钠纳米银颗粒。
实施例10:配制10mL、15mg/mL的海藻酸钠水溶液(pH12),将海藻酸钠水溶液加热磁力搅拌过夜,加热温度为45℃,磁力搅拌速度为800r/min,向海藻酸钠水溶液中逐滴滴加1.0mL的硝酸银(AgNO3,60mmol/L)溶液,伴随涡旋处理,向上述混合物中逐滴滴加1.0mL的抗坏血酸(Vc,5mg/L)溶液,伴随涡旋处理,超声处理混合体系,超声条件为:900W,15℃,1.5h,制备完毕后,避光保存,纳米银溶液用于紫外-可见(UV-Vis)分光光谱及抗菌性能测定,将海藻酸钠纳米银溶液以5000-10000rpm离心10min,弃去上清液,用蒸馏水反复洗涤3-5次,将沉淀放置于-80℃冰箱中冷冻1d,于真空冷冻干燥机-40℃冷冻干燥2d,得到海藻酸钠纳米银颗粒。
实施例11:配制10mL、15mg/mL的海藻酸钠水溶液(pH12),将海藻酸钠水溶液加热磁力搅拌过夜,加热温度为45℃,磁力搅拌速度为600r/min,向海藻酸钠水溶液中逐滴滴加0.4mL的硝酸银(AgNO3,40mmol/L)溶液,伴随涡旋处理,向上述混合物中逐滴滴加0.1mL的抗坏血酸(Vc,10mg/L)溶液,伴随涡旋处理,超声处理混合体系,超声条件为:300W,30℃,0.5h,制备完毕后,避光保存,纳米银溶液用于紫外-可见(UV-Vis)分光光谱及抗菌性能测定,将海藻酸钠纳米银溶液以5000-10000rpm离心20min,弃去上清液,用蒸馏水反复洗涤3-5次,将沉淀放置于-80℃冰箱中冷冻1d,于真空冷冻干燥机-40℃冷冻干燥2d,得到海藻酸钠纳米银颗粒。
实施例12:配制10mL、15mg/mL的海藻酸钠水溶液(pH12),将海藻酸钠水溶液加热磁力搅拌过夜,加热温度为45℃,磁力搅拌速度为1000r/min,向海藻酸钠水溶液中逐滴滴加0.4mL的硝酸银(AgNO3,50mmol/L)溶液,伴随涡旋处理,向上述混合物中逐滴滴加1.0mL的抗坏血酸(Vc,10mg/L)溶液,伴随涡旋处理,超声处理混合体系,超声条件为:300W,30℃,1.5h,制备完毕后,避光保存,纳米银溶液用于紫外-可见(UV-Vis)分光光谱及抗菌性能测定,将海藻酸钠纳米银溶液以5000-10000rpm离心20min,弃去上清液,用蒸馏水反复洗涤3-5次,将沉淀放置于-80℃冰箱中冷冻1d,于真空冷冻干燥机-40℃冷冻干燥2d,得到海藻酸钠纳米银颗粒。
实施例13:配制10mL、15mg/mL的海藻酸钠水溶液(pH12),将海藻酸钠水溶液加热磁力搅拌过夜,加热温度为50℃,磁力搅拌速度为600r/min,向海藻酸钠水溶液中逐滴滴加1.0mL的硝酸银(AgNO3,50mmol/L)溶液,伴随涡旋处理,向上述混合物中逐滴滴加0.2mL的抗坏血酸(Vc,10mg/L)溶液,伴随涡旋处理,超声处理混合体系,超声条件为:900W,30℃,1h,制备完毕后,避光保存,纳米银溶液用于紫外-可见(UV-Vis)分光光谱及抗菌性能测定,将海藻酸钠纳米银溶液以5000-10000rpm离心10min,弃去上清液,用蒸馏水反复洗涤3-5次,将沉淀放置于-80℃冰箱中冷冻1d,于真空冷冻干燥机-40℃冷冻干燥2d,得到海藻酸钠纳米银颗粒。
实施例14:配制10mL、15mg/mL的海藻酸钠水溶液(pH12),将海藻酸钠水溶液加热磁力搅拌过夜,加热温度为45℃,磁力搅拌速度为800r/min,向海藻酸钠水溶液中逐滴滴加1.0mL的硝酸银(AgNO3,50mmol/L)溶液,伴随涡旋处理,向上述混合物中逐滴滴加0.1mL的抗坏血酸(Vc,10mg/L)溶液,伴随涡旋处理,超声处理混合体系,超声条件为:300W,15℃,1.5h,制备完毕后,避光保存,纳米银溶液用于紫外-可见(UV-Vis)分光光谱及抗菌性能测定,将海藻酸钠纳米银溶液以5000-10000rpm离心10min,弃去上清液,用蒸馏水反复洗涤3-5次,将沉淀放置于-80℃冰箱中冷冻1d,于真空冷冻干燥机-40℃冷冻干燥2d,得到海藻酸钠纳米银颗粒。
实施例15:配制10mL、15mg/mL的海藻酸钠水溶液(pH12),将海藻酸钠水溶液加热磁力搅拌过夜,加热温度为45℃,磁力搅拌速度为1000r/min,向海藻酸钠水溶液中逐滴滴加0.4mL的硝酸银(AgNO3,50mmol/L)溶液,伴随涡旋处理,向上述混合物中逐滴滴加0.2mL的抗坏血酸(Vc,10mg/L)溶液,伴随涡旋处理,超声处理混合体系,超声条件为:300W,15℃,1.5h,制备完毕后,避光保存,纳米银溶液用于紫外-可见(UV-Vis)分光光谱及抗菌性能测定,将海藻酸钠纳米银溶液以5000-10000rpm离心10min,弃去上清液,用蒸馏水反复洗涤3-5次,将沉淀放置于-80℃冰箱中冷冻1d,于真空冷冻干燥机-40℃冷冻干燥2d,得到海藻酸钠纳米银颗粒。
图5a-图5d为不同反应条件合成纳米银的紫外-可见(UV-Vis)分光光谱图。图中:
图5a反应条件:pH 6-12,15mg/mL海藻酸钠水溶液,海藻酸钠水溶液与硝酸银溶液(50mmol/L)的体积比为100:4,海藻酸钠水溶液与抗坏血酸溶液(10mg/L)的体积比为100:2,超声条件:300W,30℃,1h;
图5b反应条件:pH 12,15mg/mL海藻酸钠水溶液,海藻酸钠水溶液与硝酸银溶液(50mmol/L)的体积比为100:0-10:1,海藻酸钠水溶液与抗坏血酸溶液(10mg/L)的体积比为100:2,超声条件:300W,30℃,1h;
图5c反应条件:pH 12,15mg/mL海藻酸钠水溶液,海藻酸钠水溶液与硝酸银溶液(50mmol/L)的体积比为100:4,海藻酸钠水溶液与抗坏血酸溶液(10mg/L)的体积比为100:0-10:1,超声条件:300W,30℃,1h;
图5d反应条件:pH 12,15mg/mL海藻酸钠水溶液,海藻酸钠水溶液与硝酸银溶液(50mmol/L)的体积比为100:0,海藻酸钠水溶液与抗坏血酸溶液(10mg/L)的体积比为100:0–100:5,超声条件:300W,30℃,1h;
由于纳米银的表面等离子体共振(SPR)的激发,纳米银的尺寸和分布可以通过UV-Vis光谱进行简单和超敏感的表征。随着金属粒度的增加,SPR吸收带向更高的波长方向移动。此外,纳米银的聚集导致吸收峰强度的降低以及高波长处的明显拖尾。记录纳米银的UV-Vis光谱,以评估不同反应条件对纳米银合成的影响。一般而言,直径小于5nm的银颗粒的吸收带出现在400nm处,当颗粒直径超过10nm时,吸收带变宽并向较高波长(410-450nm)移动。如图5a所示,当pH6,8和10时,UV-Vis光谱中最强吸收峰出现在418nm,当pH达到12时,最强吸收峰出现在400nm,吸收峰分布集中且对称,表明形成的纳米银具有良好的分散性,反应体系中的聚集可以忽略不计。随着pH值的增加,吸收峰强度逐渐升高。当pH值达到12时,波段朝向明显较低的波长移动,说明纳米银的粒度更小。由于离散电子能量的激发,小直径的纳米银颗粒显示出更高的光吸收水平。较高的pH值会改善海藻酸钠的溶解度,诱导碱性水解,产生更小分子量,更高亲和力和还原性的碎片,这对纳米银的合成和稳定是至关重要的。如图5b和图5c所示,吸收峰强度随着AgNO3和Vc添加比例的增加而逐渐升高,表明合成更多的纳米银,且由于海藻酸钠大分子的稳定作用,纳米银粒径大小基本未发生变化。在不存在AgNO3的情况下,如图5d所示,在400-450nm的波长范围内没有出现吸收峰,表明未形成纳米银。然而,在265nm处出现明显的吸收峰,与图5a和图5b中265nm处出现的吸收峰一致,说明该峰确实为过量的Vc吸收峰,整个体系不存在其他物质的合成峰。
Claims (7)
1.一种抗菌材料海藻酸钠-抗坏血酸纳米银的绿色快速制备方法,其特征在于,具体包括如下步骤:
(1)配制10-20mg/mL的海藻酸钠水溶液,调节pH至6-13;
(2)将海藻酸钠水溶液加热磁力搅拌过夜,加热温度为40-50℃,磁力搅拌速度为600-1000r/min;
(3)向搅拌过夜后的海藻酸钠水溶液中逐滴滴加的硝酸银溶液,伴随涡旋处理,海藻酸钠水溶液与硝酸银溶液的体积比为100:1-10:1,硝酸银溶液的摩尔浓度为40-60mmol/L;
(4)向步骤(3)得到的混合物中逐滴滴加抗坏血酸溶液,伴随涡旋处理,海藻酸钠水溶液与抗坏血酸溶液的体积比为100:1-10:1,抗坏血酸溶液的浓度为5-15mg/L;
(5)超声处理混合体系,超声条件为:100-900W,15-90℃,0.5-1.5h;
(6)将超声处理后的混合体系以5000-10000rpm离心10-30min,弃去上清液,用蒸馏水反复洗涤3-5次,将沉淀放置于-80℃冰箱中冷冻1-2d,于真空冷冻干燥机-40℃冷冻干燥1-3d,得到海藻酸钠纳米银颗粒。
2.根据权利要求1所述的一种抗菌材料海藻酸钠-抗坏血酸纳米银的绿色快速制备方法,其特征在于,步骤(1)配置得到的海藻酸钠水溶液的pH为12,浓度为15mg/mL。
3.根据权利要求2所述的一种抗菌材料海藻酸钠-抗坏血酸纳米银的绿色快速制备方法,其特征在于,步骤(2)中加热温度为45℃,磁力搅拌速度为1000r/min。
4.根据权利要求3所述的一种抗菌材料海藻酸钠-抗坏血酸纳米银的绿色快速制备方法,其特征在于,步骤(3)中海藻酸钠水溶液与硝酸银溶液的体积比为100:4,硝酸银溶液的摩尔浓度为50mmol/L。
5.根据权利要求4所述的一种抗菌材料海藻酸钠-抗坏血酸纳米银的绿色快速制备方法,其特征在于,步骤(4)中海藻酸钠水溶液与抗坏血酸溶液的体积比为100:2,抗坏血酸溶液的浓度为10mg/L。
6.根据权利要求5所述的一种抗菌材料海藻酸钠-抗坏血酸纳米银的绿色快速制备方法,其特征在于,步骤(5)中,所述超声条件为:300W,30℃,1h。
7.根据权利要求6所述的一种抗菌材料海藻酸钠-抗坏血酸纳米银的绿色快速制备方法,其特征在于,步骤(6)中将超声处理后的混合体系以5000rpm离心10min,弃去上清液,用蒸馏水反复洗涤3次,将沉淀放置于-80℃冰箱中冷冻1d,于真空冷冻干燥机-40℃冷冻干燥2d,得到海藻酸钠纳米银颗粒。
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