CN102873335A - Preparation method of temperature-sensitive water-soluble silver nanoparticles - Google Patents

Preparation method of temperature-sensitive water-soluble silver nanoparticles Download PDF

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Publication number
CN102873335A
CN102873335A CN2011101960940A CN201110196094A CN102873335A CN 102873335 A CN102873335 A CN 102873335A CN 2011101960940 A CN2011101960940 A CN 2011101960940A CN 201110196094 A CN201110196094 A CN 201110196094A CN 102873335 A CN102873335 A CN 102873335A
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solution
silver nanoparticles
preparation
pvme
sodium borohydride
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张天柱
王紫芙
顾宁
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Southeast University
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Southeast University
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Abstract

本发明公开了一种热敏水溶性银纳米颗粒的制备方法，包括以下步骤：(1)首先配制一定浓度的聚甲基乙烯基醚（PVME）水溶液；(2)加入新鲜的AgNO3溶液，不断搅拌；(3)在搅拌的同时，逐滴加入新鲜配制的NaBH4溶液;(4)搅拌过夜，即制备得到PVME包裹的银纳米粒子；(5)离心并洗涤3次，以去除多余的PVME和其他离子杂质，即得到聚甲基乙烯基醚修饰的银纳米颗粒。本发明用原位还原法制备聚甲基乙烯基醚修饰的银纳米粒子，经过PVME修饰的银纳米粒子将能够能够显著提高Ag纳米粒子在水溶液中的稳定性和分散性，实现可逆团聚的可控性，从而使Ag纳米粒子能够更好地应用在抗菌和肿瘤热疗等方面。The invention discloses a method for preparing heat-sensitive water-soluble silver nanoparticles, which comprises the following steps: (1) first preparing a certain concentration of polymethyl vinyl ether (PVME) aqueous solution; (2) adding fresh AgNO 3 solution, Stir continuously; (3) while stirring, add freshly prepared NaBH solution drop by drop; (4) stir overnight to prepare PVME-wrapped silver nanoparticles; (5) centrifuge and wash 3 times to remove excess PVME and other ionic impurities, that is, silver nanoparticles modified with polymethylvinyl ether. The present invention prepares silver nanoparticles modified by polymethylvinyl ether by in-situ reduction method, and the silver nanoparticles modified by PVME can significantly improve the stability and dispersibility of Ag nanoparticles in aqueous solution, and realize reversible agglomeration. Controllability, so that Ag nanoparticles can be better used in antibacterial and tumor hyperthermia.

Description

A kind of preparation method of heat-sensitive water-soluble silver nano-grain
Technical field
The present invention relates to the chemicals preparation field, relate to particularly a kind of preparation method of heat-sensitive water-soluble silver nano-grain.
 
Background technology
Nano silver grain has been showed very high excitation of plasma effect, and higher catalytic performance and broad spectrum antibacterial are arranged, and in catalysis, the fields such as medical and health and biomedical engineering all have potential using value.But because the fine silver nano grain surface can be high, easily oxidation and reunion limited its application in dielectric solution.TGA commonly used, mercaptoethylmaine, cysteine and polypeptide etc. are modified Nano silver grain, but the gathering of silver nano-grain still can not be avoided fully.Polymethyl vinyl ether (PVME) be nontoxic, can biocompatible material, have hydrophilic and hydrophobic amphiphilic nature.The aqueous solution of poly-methyl ethylene has bimodal low critical consolute temperature (lower critical solution temperature, LCST) curve, near 37 ℃ of the physiological temps of human body.And be easy to the PVME aqueous solution is cross-linked into three-dimensional net structure with high-energy radiation (such as gamma-rays or electron beam).Given this characteristic, the modification of PVME can significantly improve its stability in the aqueous solution and dispersed.Can be applied in better antibiotic and the aspect such as tumor thermotherapy through the Nano silver grain of modifying.
 
Summary of the invention
The object of the present invention is to provide a kind of preparation method of heat-sensitive water-soluble silver nano-grain, with polymethyl vinyl ether Nano silver grain is modified, solved in the prior art and with TGA, mercaptoethylmaine, cysteine and polypeptide etc. Nano silver grain has been modified, the problem that can not avoid fully for the gathering of silver nano-grain.
The object of the present invention is achieved like this: polymethyl vinyl ether (PVME) aqueous solution of at first preparing 1-10wt%; Adding respectively concentration is the freshly prepared AgNO of 0.03-0.1mmol/L again 3Solution (AgNO 3The PVME mass ratio 0.03-0.08 of solid and drying); Keep stirring; Subsequently, dropwise add freshly prepared NaBH 4Solution (AgNO 3With NaBH 4Molar ratio 0.2-0.8 NaBH 4It is excessive to keep), behind the reaction certain hour, centrifugation, and with intermediate water washing three times, to remove unnecessary PVME and other ionic impurities, namely obtain the silver nano-grain (PVME-Ag NPs) that polymethyl vinyl ether is modified.
Compared with prior art, the present invention has the following advantages:
A kind of Nano silver grain with heat-sensitive water-soluble of the present invention, namely prepare the Nano silver grain that polymethyl vinyl ether (PMVE) is modified with local reduction way, make the change of the solubility with temperature of Ag nano particle in solution and change, realize the controllability of reversible reunion.
The specific embodiment
The preparation method of a kind of heat-sensitive water-soluble silver nano-grain of the present invention specifically may further comprise the steps:
Step 1: at first be that 50wt% PVME original solution utilizes Rotary Evaporators evaporation 3-4h with concentration, put into again vacuum drying chamber, be heated to 50 ℃ of dried overnight.Namely get every other day dry PVME solid;
Step 2: place round-bottomed flask with this PVME solution of preparing a series of variable concentrations (1-10wt%), be accompanied by magnetic agitation;
Step 3: the freshly prepared AgNO that adds respectively again variable concentrations (0.03-0.1mmol/L) 3Solution, AgNO 3The PVME mass ratio 0.03-0.08 of solid and drying), keep stirring;
Step 4: the NaBH of the variable concentrations that rapid preparing is good fresh 4The aqueous solution (AgNO 3With NaBH 4Molar ratio 0.2-0.8), with NaBH 4The aqueous solution dropwise adds PVME and the AgNO in the round-bottomed flask 3Mixed solution in, lasting stirring is spent the night;
Step 5: centrifugation, remove supernatant, and water dissolves again.Triplicate.
Embodiment 1
1. the PVME that takes by weighing the 0.2000g drying places round-bottomed flask, adds the ultra-pure water of 3.8000g, is made into the solution of 5wt%, puts into stirrer, and normal temperature lower magnetic force stir about 3h is to fully dissolving;
2. take by weighing the AgNO of 0.0100g 3Solid places test tube, adds the ultra-pure water wiring solution-forming of 5.0000g, with AgNO 3Solution is transferred in the round-bottomed flask of the above-mentioned PMVE of filling solution, mixes under stirring;
3. take by weighing 0.0040g purity and be 96% NaBH 4Solid places test tube, adds the ultra-pure water wiring solution-forming of 5.0000g, dropwise with NaBH 4Solution joins PVME and the AgNO in the above-mentioned round-bottomed flask 3In the mixed solution, and keep stirring;
4. stir and spend the night;
5. centrifugal and wash 3 times, to remove unnecessary PVME and other ionic impurities, the average grain diameter of the Nano silver grain of acquisition is about 12nm;
Embodiment 2
1. the PVME that takes by weighing the 0.3000g drying places round-bottomed flask, adds the ultra-pure water of 3.8000g, is made into the solution of 7.3wt%, puts into stirrer, and normal temperature lower magnetic force stir about 3h is to fully dissolving;
2. take by weighing the AgNO of 0.0200g 3Solid places test tube, adds the ultra-pure water wiring solution-forming of 5.0000g, with AgNO 3Solution is transferred in the round-bottomed flask of the above-mentioned PMVE of filling solution, mixes under stirring;
3. take by weighing 0.0040g purity and be 96% NaBH 4Solid places test tube, adds the ultra-pure water wiring solution-forming of 5.0000g, dropwise with NaBH 4Solution joins PMVE and the AgNO in the above-mentioned round-bottomed flask 3In the mixed solution, and keep stirring;
4. stir and spend the night;
5. centrifugal and wash 3 times, to remove unnecessary PVME and other ionic impurities, the average grain diameter of the Nano silver grain of acquisition is about 22nm;
Embodiment 3
1. the PVME that takes by weighing the 0.2000g drying places round-bottomed flask, adds the ultra-pure water of 3.8000g, is made into the solution of 5wt%, puts into stirrer, and the about 3h of magnetic agitation is to fully dissolving;
2. take by weighing the AgNO of 0.0055g 3Solid places test tube, adds the ultra-pure water wiring solution-forming of 5.0000g, with AgNO 3Solution is transferred in the round-bottomed flask of the above-mentioned PMVE of filling solution, mixes;
3. take by weighing the NaBH of 0.0022g 96% 4Solid places test tube, adds the ultra-pure water wiring solution-forming of 5.0000g, dropwise with NaBH 4Solution joins PMVE and the AgNO in the above-mentioned round-bottomed flask 3In the mixed solution, and keep stirring;
4. stir and spend the night;
5. centrifugal and wash 3 times, to remove unnecessary PVME and other ionic impurities, the average grain diameter of the Nano silver grain of acquisition is about 11nm;
Above-described embodiment just is to allow the one of ordinary skilled in the art can understand content of the present invention and according to this enforcement for technical conceive of the present invention and characteristics being described, its objective is, can not limit protection scope of the present invention with this.Variation or the modification of every equivalence that the essence of content is made according to the present invention all should be encompassed in protection scope of the present invention.

Claims (5)

1.一种热敏水溶性银纳米颗粒的制备方法，其特征在于，包括以下步骤： 1. a preparation method of thermosensitive water-soluble silver nanoparticles, is characterized in that, comprises the following steps:     步骤一：首先配制浓度为1wt-10wt%的聚甲基乙烯基醚水溶液，置于圆底烧瓶中，并伴随着磁力搅拌； Step 1: First, prepare a polymethyl vinyl ether aqueous solution with a concentration of 1wt-10wt%, place it in a round bottom flask, and stir it with a magnetic force;   步骤二：再加入浓度为0.03-0.1 mmol/L的新鲜配制的硝酸银溶液，硝酸银固体与干燥的聚甲基乙烯基醚质量比为0.03-0.08，保持搅拌； Step 2: Add freshly prepared silver nitrate solution with a concentration of 0.03-0.1 mmol/L, the mass ratio of silver nitrate solid to dry polymethyl vinyl ether is 0.03-0.08, and keep stirring;   步骤三：在试管中快速配制好新鲜的不同浓度的硼氢化钠水溶液，硝酸银与硼氢化钠物质的量比0.2-0.8，还原剂硼氢化钠保持过量，再将硼氢化钠水溶液逐滴加入到圆底烧瓶中聚甲基乙烯基醚和硝酸银的混合溶液中，持续搅拌过夜； Step 3: Quickly prepare fresh sodium borohydride aqueous solutions of different concentrations in the test tube, the ratio of silver nitrate to sodium borohydride is 0.2-0.8, the reducing agent sodium borohydride is kept in excess, and then the sodium borohydride aqueous solution is added dropwise In the mixed solution of polymethyl vinyl ether and silver nitrate in the round-bottomed flask, keep stirring overnight; 步骤四：离心沉淀，除去上清液，并用水重新溶解，重复三次，以去除多余的聚甲基乙烯基醚和其他离子杂质，即得到聚甲基乙烯基醚修饰的银纳米颗粒。 Step 4: Centrifuge to precipitate, remove the supernatant, and redissolve with water, repeat three times to remove excess polymethylvinyl ether and other ionic impurities, and obtain polymethylvinyl ether-modified silver nanoparticles. 2.根据权利要求1所述的热敏水溶性银纳米颗粒的制备方法，其特征在于，所述步骤一中所用的聚甲基乙烯基醚，为线性的、支化的或交联的，重均分子量在2万到5万之间，分子量分布宽度为2.5。 2. the preparation method of heat-sensitive water-soluble silver nanoparticles according to claim 1, is characterized in that, the polymethyl vinyl ether used in described step 1 is linear, branched or crosslinked, The weight average molecular weight is between 20,000 and 50,000, and the molecular weight distribution width is 2.5. 3.根据权利要求1所述的热敏水溶性银纳米颗粒的制备方法，其特征在于，所述步骤一中所用的圆底***容积为100mL。 3. the preparation method of thermosensitive water-soluble silver nanoparticles according to claim 1, is characterized in that, the volume of the round bottom flask used in the said step 1 is 100mL. 4.根据权利要求1所述的热敏水溶性银纳米颗粒的制备方法，其特征在于，所述步骤二中，是在不断搅拌的同时，逐滴加入硼氢化钠溶液。 4. the preparation method of heat-sensitive water-soluble silver nanoparticles according to claim 1, is characterized in that, in described step 2, is to add sodium borohydride solution dropwise while constantly stirring. 5.   根据权利要求1所述的所述的热敏水溶性银纳米颗粒的制备方法，其特征在于，所述步骤三中，加入硼氢化钠溶液，以硼氢化钠还原硝酸银，反应的温度在-10℃-25℃之间。 5. the preparation method of the described heat-sensitive water-soluble silver nanoparticle according to claim 1, it is characterized in that, in described step 3, add sodium borohydride solution, reduce silver nitrate with sodium borohydride, the temperature of reaction Between -10°C and 25°C.
CN2011101960940A 2011-07-14 2011-07-14 Preparation method of temperature-sensitive water-soluble silver nanoparticles Pending CN102873335A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104588679A (en) * 2015-01-15 2015-05-06 黑龙江大学 Preparation method of nano silver-nickel alloy powder
CN109880572A (en) * 2019-01-29 2019-06-14 安徽天光传感器有限公司 A kind of preparation method of sensor high-conductive heat-resistant conducting resinl

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006336060A (en) * 2005-06-01 2006-12-14 Sumitomo Metal Mining Co Ltd Nickel particle powder and production method therefor
CN101077528A (en) * 2006-05-26 2007-11-28 徐健宏 Method for manufacturing ultrafine nanometer precious metal solution
CN101522557A (en) * 2006-09-29 2009-09-02 Lg化学株式会社 Ink for ink jet printing and method for preparing metal nanoparticles used therein
CN101758244A (en) * 2010-01-29 2010-06-30 浙江大学 Preparation method for water-soluble precious metal nano particle
CN101990475A (en) * 2008-04-28 2011-03-23 塔塔化学有限公司 A process for the preparation of silver nano particles

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006336060A (en) * 2005-06-01 2006-12-14 Sumitomo Metal Mining Co Ltd Nickel particle powder and production method therefor
CN101077528A (en) * 2006-05-26 2007-11-28 徐健宏 Method for manufacturing ultrafine nanometer precious metal solution
CN101522557A (en) * 2006-09-29 2009-09-02 Lg化学株式会社 Ink for ink jet printing and method for preparing metal nanoparticles used therein
CN101990475A (en) * 2008-04-28 2011-03-23 塔塔化学有限公司 A process for the preparation of silver nano particles
CN101758244A (en) * 2010-01-29 2010-06-30 浙江大学 Preparation method for water-soluble precious metal nano particle

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104588679A (en) * 2015-01-15 2015-05-06 黑龙江大学 Preparation method of nano silver-nickel alloy powder
CN109880572A (en) * 2019-01-29 2019-06-14 安徽天光传感器有限公司 A kind of preparation method of sensor high-conductive heat-resistant conducting resinl

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