| Publication number | CN104889419 A |
| Publication type | Application |
| Application number | CN 201510255581 |
| Publication date | 9 Sep 2015 |
| Filing date | 18 May 2015 |
| Priority date | 18 May 2015 |
| Also published as | CN104889419B |
| Publication number | 201510255581.8, CN 104889419 A, CN 104889419A, CN 201510255581, CN-A-104889419, CN104889419 A, CN104889419A, CN201510255581, CN201510255581.8 |
| Inventors | 史昕怡, 潘林武 |
| Applicant | 湖州品创孵化器有限公司 |
| Export Citation | BiBTeX, EndNote, RefMan |
| Patent Citations (6), Non-Patent Citations (3), Classifications (4), Legal Events (4) | |
| External Links: SIPO, Espacenet | |
技术领域 TECHNICAL FIELD
[0001] 本发明涉及一种纳米银的生物合成方法，尤其是用芒果皮提取物和金钱草提取物合成纳米银。 [0001] The present invention relates to a method for the biosynthesis of silver nanoparticles, especially with mango extract and loosestrife bark extract synthetic nano-silver.
背景技术 Background technique
[0002] 纳米银粒子具有独特的物理化学性质，广泛应用于催化、光电学、光学、生物科学及制药等方面。 [0002] The silver nanoparticles have unique physical and chemical properties, widely used in catalysis, optoelectronics, optical, biological sciences and pharmaceutical aspects. 因此，研宄纳米银的制备方法具有重要的意义。 Therefore, the preparation method of study based on nano-silver has important significance. 目前，纳米银粒子可以通过物理(蒸气一冷凝法、球磨法、溅射法、放电爆炸法)、化学(液相反应法、气相反应法、模板合成法)、光催化以及生物等方法制备。 Currently, silver nanoparticles can be physical (a vapor condensation, milling, sputtering, discharge explosion method), chemical (liquid phase reaction, gas phase reaction method, template synthesis), photocatalysis and biological methods such as preparation. 与物化方法相比，生物法因具有高效、快速、稳定、简单易行、环境友好、无毒及价格低廉等诸多优点而被众多研宄者关注。 Compared with the physico-chemical method, biological method because an efficient, fast, stable, simple, environmentally friendly, non-toxic and low price and many other advantages are the concern of many who study based. 生物法制备纳米银粒子主要指利用生物有机物作为还原剂和保护剂，通过将A g NO 3溶液中的A g +还原成A g Q，生成纳米银粒子。 Biological Preparation of silver nanoparticles mainly refers to the use of organic matter as a reducing agent and protection of biological agents, by the A g NO 3 solution A g + is reduced to A g Q, generate silver nanoparticles.
[0003] 采用果皮提取物制备纳米银粒子不仅高效快速，还能废物利用，有利于环保，植物叶及种子资源丰富，具有极强的再生能力，利用果皮、植物叶及种子等的提取物制备纳米银粒子极具潜力。 [0003] The peel extract nano silver particles is not only fast and efficient, but also recycling, in favor of rich green, plant leaves and seeds of resources, with a strong ability to regenerate prepared using peel, seed and other plant leaves and extracts Nano silver particles with great potential. 与微生物相比，采用果皮及植物制备银粒子虽然更为快速，但目前关于其研宄却很少。 Compared with microorganisms, plants use peel and preparation of silver particles, although more rapid, but rarely on their research traitor. 现有技术公开了用风干的香蕉皮、柿子树叶、红木树叶、甜橙皮等成功制得纳米银粒子。 The prior art discloses the use of dried banana peel, persimmon leaves, mahogany leaves, orange skin and so successfully prepared silver nanoparticles. 纳米银粒子的形貌和粒径直接影响其抑菌及光催化能力，制备形貌和粒径可控的纳米银粒子对其应用有极大的意义。 The morphology and particle size of silver nanoparticles directly affect its antibacterial and photocatalytic ability, morphology and particle size controlled preparation of silver nanoparticles has great significance to its application. 采用不同的生物材料可能会影响制备的纳米银粒子的形貌。 Using different biological material that may affect the morphology of the prepared silver nanoparticles. 虽然目前生物法尚不能精确控制所制备的纳米银粒子的粒径，但关于此方面的研宄较多，影响粒径的因素主要有PH值、生物材料量、温度及反应时间。 Although the biological method still can not precisely control the particle size of the prepared silver nanoparticles, but on this aspect of the study based on many factors affect particle size mainly PH value, biological materials, temperature and reaction time. 研宄发现，随着pH值升高，制备出的银粒子粒径越小。 Research traitor found that as pH increases, the prepared silver particle size is smaller. 增大提取物的量，会出现粒子粒径增大及减小两种相反的结果。 Increasing the amount of the extract appears to reduce the particle size increases, and the two opposite result. 随着反应温度升高，生成的纳米银粒子粒径越小。 As the reaction temperature increases, the resulting nano silver particle size is smaller.
[0004] 现有技术公开了一种用芒果皮制备纳米银粒子的方法。 [0004] The prior art discloses a mango peel nano silver particles approach. 芒果皮作为芒果工业化加工生产中产生的加工副产物，一般被抛弃，既造成资源的巨大浪费，又污染环境。 Mango mango skin as a process by-product generated in the production of industrial processing, are generally abandoned, both resulting in a huge waste of resources, but also pollute the environment. 据研宄，芒果皮中含有大量黄酮化合物、多酚化合物和多糖，都是很好的还原剂。 According to the study based on mango skin contains large amounts of flavonoids, polyphenols and polysaccharides, they are good reducing agent. 实验研宄了以食品工业下脚料芒果皮作为还原剂和分散剂，合成分散性很好的纳米银。 Experimental study based on a mango peel waste in the food industry as a reducing agent and a dispersant, a good dispersion of synthetic nano-silver. 研宄表明，PH值为1 1， 芒果皮提取物的添加量为Q . I m L，硝酸银溶液浓度为Q . 5 mM，反应条件为8 Q°C，水浴I 5m i η时，经紫外可见分光光度法和T EM表征合成的纳米银的粒径最小，为7 η m(± 2 3%)。 Research traitor showed, PH value 11, Q mango bark extract dosage of. I m L, the concentration of silver nitrate solution as Q. 5 mM, reaction conditions 8 Q ° C, water bath when I 5m i η by UV-visible spectrophotometry and T EM characterization of synthetic nano-silver particle size minimum for 7 η m (± 2 3%). 但是该方法反应温度高，PH高，在大量工业化生产中能耗比较高。 While this method the reaction temperature is high, PH high, industrial production in a large number of relatively high energy consumption.
[0005] 本发明旨在提供一种纳米银的生物合成方法，利用芒果皮和金钱草，可以在较低的温度下，生产粒径小，分布范围窄，形态呈较规则球形的纳米银粒子。 [0005] The present invention aims to provide a method for the biosynthesis of silver nanoparticles using mango leather and loosestrife, at lower temperatures can produce small particle size, narrow distribution, morphology was more regular spherical silver nanoparticles .
发明内容 SUMMARY OF THE INVENTION
[0006] 本发明的目的是提供一种纳米银的生物合成方法，利用芒果皮提取物和金钱草提取物，可以在较低的温度下，偏中性的反应环境小，生产粒径6nm左右，分布范围窄的纳米银粒子。 [0006] The object of the present invention is to provide a method for the biosynthesis of silver nanoparticles, the use of mango bark extract and extract money grass can be at a lower temperature, the reaction neutral in a small environment, production diameter of about 6nm , narrow distribution of nano-silver particles.
[0007] 纳米银粒子具有较强的抗菌能力，广泛应用于临床医学，如外科手术以及伤口愈合等，未来有潜力用于消炎、抗肿瘤、妇科以及再生医学等方面。 [0007] silver nanoparticles has strong antibacterial ability, widely used in clinical medicine, such as surgery and wound healing, the future potential for anti-inflammatory, anti-tumor, gynecological and regeneration medicine. 目前，纳米银粒子的抑菌机理尚不十分清楚，可能的机理可分为：（1 )纳米银粒子溶于水中会转化成银离子，杀死病原体；（2 )纳米银粒子在细菌细胞膜外大量累积，会改变细胞膜的渗透率，导致细菌死亡； (3)纳米银粒子具有较小的粒径和大的比表面积，因此，纳米银粒子能轻易破坏细胞膜，进入细胞内，在细胞质中转化成银离子，损坏胞内结构。 Currently, the antibacterial mechanism of silver nanoparticles is not very clear, possible mechanisms can be divided into: (1) Nano silver particles dissolved in water will be converted into silver ions kill pathogens; (2) the nano silver particles in the bacterial outer membrane a lot of accumulation, will change the permeability of cell membranes, leading to bacterial death; (3) Nano silver particles have a smaller particle size and large surface area, so that silver nanoparticles can easily damage the cell membrane, into the cell, transformed in the cytoplasm a silver ion, damage intracellular structures.
[0008] 纳米银粒子的抑菌能力取决于多方面的因素：（1 )形貌。 [0008] The antibacterial activity of silver nanoparticles depends on many factors: (1) topography. 相同表面积的纳米银粒子处理大肠杆菌，不同的形貌其抑菌能力有差别，不同形状也许会导致其起有效作用表面积不同，影响抑菌能力。 The same surface area of nano-silver particles treated E. coli, the different morphologies of their antibacterial ability differences, different shapes may lead to different surface play an effective role, affecting antibacterial activity. （2)粒径。 (2) particle size. 银粒子粒径越小，抑菌能力越强。 Silver particle size is smaller, the stronger the antibacterial ability. （3)制备方法。 (3) Preparation. 生物法制备的纳米银粒子的抑菌能力高于化学法所制备的纳米银粒子。 Antibacterial biological preparedness Nano silver particles is higher than silver nanoparticles chemically prepared.
[0009] 纳米银粒子在反应过程中主要经历生成、团聚、破碎及溶解4个阶段，生物法制备纳米银粒子具有高效、快速且稳定性高等特点，因而生成及团聚会在短时间内完成且破碎及溶解过程不明显，反应在较短时间内就达到平衡。 [0009] The nano silver particles in the reaction process is mainly generated through agglomeration, crushing and dissolving four stages, biological Preparation of silver nanoparticles is an efficient, fast and high stability, thus generating and reunion will be completed in a short time and crushing and dissolution process is not obvious, the reaction in a relatively short time to reach equilibrium. 植物及果皮中的醇类、醚、羧酸、脂肪族及芳香族化合物等有机物有可能在反应中充当还原剂及保护剂。 Plants and peel alcohols, ethers, carboxylic acids, aliphatic and aromatic compounds and other organic matter likely to act as a reducing agent and protecting agent in the reaction.
[0010] 现有技术都是单一使用一种植物原料进行提取，本发明人尝试用两种或者两种以上的植物提取液，发现芒果皮提取物和金钱草提取物共同作用下，能达到某种协同效果，显著优化反应条件。 [0010] A prior art single-use plant material is extracted, the present inventors attempted extract using two or more kinds of plants, found under mango skin extract and extract of Lysimachia joint action, to achieve a Synergistic effects, significantly optimizing the reaction conditions. 具体而言，是降低反应温度，让PH偏中性，缩小纳米银粒子的直径。 Specifically, the reaction temperature is lowered, so that PH neutral pH, reduced diameter silver nanoparticles.
[0011] 为了实现上述的目的，本发明采用了以下的技术方案： 一种纳米银的生物合成方法，其步骤如下： (1) 制备芒果皮提取液； (2) 制备金钱草提取液； (3) 混合反应： 取芒果皮提取液，金钱草提取液，与9-10倍重量的0. 5 m M的硝酸银溶液混合，调节硝酸银溶液的pH值为8. 0, 50-55°C反应12-15min。 [0011] To achieve the above object, the present invention employs the following technical solutions: Biosynthesis method of nano-silver, which is as follows: (1) Preparation of mango bark extract liquid; (2) Preparation of loosestrife extract; ( 3) Reaction mix: Mango Bark was taken, Desmodium extract, mixed with a silver nitrate solution of 9-10 times the weight of 0. 5 m M, the silver nitrate solution to adjust the pH value of 8. 0, 50-55 ° C-reactive 12-15min.
[0012] 作为优选，步骤（1)为：称取新鲜芒果皮，加水量为芒果皮重量的2倍榨成汁，过滤，4 °C保存备用； 作为优选，步骤（2)为：取干药材金钱草，加水量为金钱草重量的8倍，经85-90 °C水浴提取3-4 h，过滤，得金钱草提取液； 作为优选，步骤（3)为：取1倍重量芒果皮提取液，0. 15-0. 2倍重量金钱草提取液，与9-10倍重量的0. 5 mM的硝酸银溶液混合，调节硝酸银溶液的pH值为8. 0, 5 (TC反应12_15min〇 [0012] Preferably, the step (1) as follows: Weigh fresh mango peel, add water to 2 times the weight of the mango skin pressed into juice, filtered, 4 ° C to save the backup; Preferably, the step (2): Take dry herbs loosestrife, Lysimachia 8 times the amount of water weight by 85-90 ° C water extraction 3-4 h, filtration, loosestrife extract; Preferably, the step (3): Take 1 times the weight of the mango skin extract, 0. 15-0. 2 times the weight Desmodium extract, mixed with a silver nitrate solution of 9-10 times the weight of 0. 5 mM, pH adjusted value of the silver nitrate solution 8. 0, 5 (TC Reaction 12_15min〇
[0013] 本发明的有益之处在于： 1.本发明采用芒果皮作为生产原料，芒果皮一般被抛弃，既造成资源的巨大浪费，又污染环境，利用本发明可以变废为宝。 [0013] The usefulness of the present invention is that: 1. The invention uses mango peel as raw material, the mango skin generally been abandoned, both resulting in a huge waste of resources, but also pollute the environment, the use of the present invention may be turning waste into treasure.
[0014] 2.本发明的合成方法具有高效、快速、稳定、简单易行、环境友好、无毒及价格低廉的优点3.本发明的合成方法需要温度低，pH偏中性，制备出分散性能佳，粒径极小，分布范围极窄，抑菌效果非常好的纳米银粒子。 [0014] A method for synthesis of the present invention is an efficient, fast, stable, simple, environmentally friendly, non-toxic and inexpensive synthetic methods advantages and 3. The present invention requires low temperature, pH neutral pH, prepared by dispersing good performance, small particle size, very narrow range, the effect is very good antibacterial silver nanoparticles.
具体实施方式 detailed description
[0015] 实施例1: 一种纳米银的生物合成方法，其步骤如下： 制备芒果皮提取液： 称取新鲜芒果皮，加水量为芒果皮重量的2倍榨成汁，过滤，4 °C保存备用； 制备金钱草提取液： 取干药材金钱草，加水量为金钱草重量的8倍，经85 °C水浴提取4 h得金钱草提取液， 过滤，备用； 取1倍重量芒果皮提取液，〇. 15倍重量金钱草提取液，与10倍重量0. 5 mM的硝酸银溶液混合，调节硝酸银溶液的pH值为8. 0, 50°C反应12min。 [0015] Example 1: A method of biosynthesis of silver nanoparticles, the following steps: preparation of mango peel extract solution: Weigh fresh mango peel, add water to 2 times the weight of the mango skin pressed into juice, filtered, 4 ° C Save backup; Preparation loosestrife extract: Take dried herbs loosestrife, Lysimachia 8 times the amount of water weight by 85 ° C water bath for 4 h to obtain money grass extract extract, filter, spare; take 1 times the weight of mango bark extract solution, square. Desmodium extract 15 times by weight, mixed with 10 times the weight of 0. 5 mM silver nitrate solution, adjusting the pH value of the silver nitrate solution 8. 0, 50 ° C the reaction 12min.
[0016] 实施例2: 一种纳米银的生物合成方法，其步骤如下： 制备芒果皮提取液： 称取新鲜芒果皮，加水量为芒果皮重量的2倍榨成汁，过滤，4 °C保存备用； 制备金钱草提取液： 取干药材金钱草，加水量为金钱草重量的8倍，经90 °C水浴提取3 h得金钱草提取液， 过滤，备用； 取1倍重量芒果皮提取液，〇. 2倍重量金钱草提取液，与9倍重量0. 5 m M的硝酸银溶液混合，调节硝酸银溶液的pH值为8. 0, 55°C反应15min。 2 [0016] Example: biosynthetic method of nano-silver, which is as follows: Preparation of mango peel extract solution: Weigh fresh mango peel, add water to 2 times the weight of the mango skin pressed into juice, filtered, 4 ° C Save backup; Preparation loosestrife extract: Take dried herbs loosestrife, Lysimachia 8 times the amount of water weight by 90 ° C water bath for 3 h to obtain money grass extract extract, filter, spare; take 1 times the weight of mango bark extract solution, square. Desmodium extract 2 times by weight, and 9-fold weight of 0. 5 m Mixed M silver nitrate solution, adjusting the pH value of the silver nitrate solution 8. 0, 55 ° C the reaction 15min.
[0017] 实施例3: 一种纳米银的生物合成方法，其步骤如下： 制备芒果皮提取液： 称取新鲜芒果皮，加水量为芒果皮重量的2倍榨成汁，过滤，4 °C保存备用； 制备金钱草提取液： 取干药材金钱草，加水量为金钱草重量的8倍，经87 °C水浴提取4 h得金钱草提取液， 过滤，备用； 取1倍重量芒果皮提取液，〇. 18倍重量金钱草提取液，与10倍重量0. 5 mM的硝酸银溶液混合，调节硝酸银溶液的pH值为8. 0, 53°C反应14min。 3 [0017] Example: biosynthetic method of nano-silver, which is as follows: Preparation of mango peel extract solution: Weigh fresh mango peel, add water to 2 times the weight of the mango skin pressed into juice, filtered, 4 ° C Save backup; Preparation loosestrife extract: Take dried herbs loosestrife, Lysimachia 8 times the amount of water weight by 87 ° C water bath for 4 h to obtain money grass extract extract, filter, spare; take 1 times the weight of mango bark extract solution, square. Desmodium extract 18 times by weight, mixed with 10 times the weight of 0. 5 mM silver nitrate solution, adjusting the pH value of the silver nitrate solution 8. 0, 53 ° C the reaction 14min.
[0018] 实施例4: 一种纳米银的生物合成方法，其步骤如下： 制备芒果皮提取液： 称取新鲜芒果皮，加水量为芒果皮重量的2倍榨成汁，过滤，4 °C保存备用； 制备金钱草提取液： 取干药材金钱草，加水量为金钱草重量的8倍，经89 °C水浴提取3 h得金钱草提取液， 过滤，备用； 取1倍重量芒果皮提取液，〇. 16倍重量金钱草提取液，与9倍重量0. 5 mM的硝酸银溶液混合，调节硝酸银溶液的pH值为8. 0, 51°C反应13min。 [0018] Example 4: Biosynthesis of silver nanoparticles method, the following steps: preparation of mango peel extract solution: Weigh fresh mango peel, add water to 2 times the weight of the mango skin pressed into juice, filtered, 4 ° C Save backup; Preparation loosestrife extract: Take dried herbs loosestrife, Lysimachia 8 times the amount of water weight by 89 ° C water bath for 3 h to obtain money grass extract extract, filter, spare; take 1 times the weight of mango bark extract solution, square. Desmodium extract 16 times by weight, mixed with 9 times by weight of 0. 5 mM silver nitrate solution, adjusting the pH value of the silver nitrate solution 8. 0, 51 ° C the reaction 13min.
[0019] 实施例5: 一种纳米银的生物合成方法，其步骤如下： 制备芒果皮提取液： 称取新鲜芒果皮，加水量为芒果皮重量的2倍榨成汁，过滤，4 °C保存备用； 制备金钱草提取液： 取干药材金钱草，加水量为金钱草重量的8倍，经86 °C水浴提取4 h得金钱草提取液， 过滤，备用； 取1倍重量芒果皮提取液，〇. 19倍重量金钱草提取液，与10倍重量0. 5 mM的硝酸银溶液混合，调节硝酸银溶液的pH值为8. 0, 54°C反应12min。 [0019] Example 5: A method of biosynthesis of silver nanoparticles, the following steps: preparation of mango peel extract solution: Weigh fresh mango peel, add water to 2 times the weight of the mango skin pressed into juice, filtered, 4 ° C Save backup; Preparation loosestrife extract: Take dried herbs loosestrife, Lysimachia 8 times the amount of water weight by 86 ° C water bath for 4 h to obtain money grass extract extract, filter, spare; take 1 times the weight of mango bark extract liquid, square 19 times the weight of money grass extract, and 10 times the weight of the mixed 0. 5 mM silver nitrate solution, adjusting the pH value of the silver nitrate solution 8. 0, 54 ° C reaction 12min.
[0020] 实施例6: 对实施例1-5得到的纳米银溶液进行形态的表征。 [0020] Example 6: nano silver solution obtained in Example 1-5 were characterized form.
[0021] 采用紫外一可见分光光度法，透射电镜（τ EM)表征不同实施例下合成的纳米银溶液，结果如表1所示。 [0021] The UV-visible spectrophotometry, transmission electron microscopy (τ EM) characterization of nano silver solution synthesized under a different embodiment, the results shown in Table 1.
[0022] 表1 [0022] Table 1
实施例7抑菌效果测评： 采用牛津杯法进行抑菌试验。 Example 7 Evaluation antibacterial effect: Antibacterial test conducted using the Oxford cup method. 放置直径为8_的牛津杯，加入实施例1-5合成的纳米银溶液。 Place diameter 8_ Oxford cup, adding nano silver solution synthesized in Example 1-5. 放入3 7 °C培养箱中培养2 4 h，用游标卡尺测量抑菌圈直径。 Add 3 7 ° C incubator for 2 4 h, inhibition zone diameter measurements with calipers. 用芒果皮提取液和金钱草提取液混合物作对照。 Bark with mango extract liquid and loosestrife mixture as a control. 测试结果见表2所示。 The test results are shown in Table 2.
[0023] 表2 [0023] Table 2
从上表可以明显的看出，本发明的纳米银溶液具有非常好的抑菌效果。 Can be clearly seen from the table, the nanosilver solution of the present invention has a very good antibacterial effect.
[0024] 尤其是实施例2的纳米银溶液，为本发明的最佳实施例。 [0024] In particular preferred embodiments of the nanosilver solution of Example 2, the present invention.
[0025] 以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此， 任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。 [0025] The above is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any skilled in the art in the art within the technical scope of the present invention is disclosed, according to the present invention The technical program and its inventive concept to be equivalents or change, should fall within the scope of the present invention.
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| Date | Code | Event | Description |
|---|---|---|---|
| 9 Sep 2015 | C06 | Publication | |
| 7 Oct 2015 | C10 | Entry into substantive examination | |
| 16 Nov 2016 | C41 | Transfer of patent application or patent right or utility model | |
| 4 Jan 2017 | C14 | Grant of patent or utility model |
