纳米金的制备及其化妆品中的应用研究
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摘要
本论文研究了特定尺寸纳米金的制备表征及其被高温高压处理后其紫外吸收光谱的变化,并通过MTT法、3H-TdR掺入试验法研究了粒径在15-20nm的纳米金对细胞的毒性,本论文的目的是为纳米金用于化妆品提供实验依据,故选择了人体皮肤正常细胞(人体表皮细胞、HSF细胞)、癌细胞(Hela细胞、K562细胞、CHO细胞)为研究对象。
通过化学还原法制备出不同粒径的纳米金颗粒,利用紫外可见分光光度计和透射电子显微镜对纳米金颗粒的形貌及尺寸进行表征。讨论了不同条件对纳米金制备的影响。结果表明, Na3C6H5O7为还原剂制得纳米金颗粒粒径在15-20nm之间,NaBH4为还原剂制得的纳米金颗粒粒径在3-10nm之间;柠檬酸钠与氯金酸的摩尔比为1.5:1时最佳;Na3C6H5O7为还原剂时,采用HAuCl4溶液加入到加热的Na3C6H5O7与聚乙烯吡咯烷酮(PVP)混合溶液比Na3C6H5O7溶液加入到加热的HAuCl4与PVP混合溶液制得的纳米金溶胶的颗粒分散性好,粒径小且更均一。粒径在15-20nm的纳米金经金高温高压处理其紫外可见吸收光谱分析,总体来说纳米金经高温高压处理变化很小,故细胞毒性试验过程中纳米金的灭菌可以使用高温高压的方法。
通过细胞毒性试验得:纳米金对人体皮肤正常细胞在一定浓度范围内均可促进细胞增殖,具有剂量依赖性和时间依赖性,在小于50ηmol/L时,随浓度的增加,其对细胞增殖的促进作用增加,在50ηmol/L时,对细胞增殖表现为最强的显著性促进作用,而后随浓度的增加,促进作用减弱,并逐步转化为对细胞增殖的抑制作用。纳米金对癌细胞作用,在浓度小于50ηmol/L时细胞活性均没有发生明显变化,在浓度大于50ηmol/L时,随浓度的增加,对细胞抑制作用增强。通过将纳米金加入到化妆品的基本配方中,制备出了稳定的乳状液,说明纳米金对乳状液的稳定性状不会产生影响。
The paper studied on the Synthesis and characterization of gold nanoparticles and the change of UV-visible absorption spectra under high temperature and high pressure treatment. And detect toxic effect of gold nanoparticles with diameter between 15nm and 20nm by MTT assay and 3H-TdR incorporation method. The purpose is to provide experimental evidence for gold nanoparticles applied in cosmetics. So choose normal cell of Human skin(human epidermal cell, Human hypertrophic scar derived fibroblasts also called HSF) and cancer cell(Hela, K562, CHO) were chosen as experi mental subjects.
Gold nano-particles with various diameters were prepared by chemical reduction, UV-Vis spectroscopy and transmission electron microscopy(TEM)were used to characterize the morphology and size of the prepared Au nanoparticles, The influence of the different syhthetic condition have been studied. The results show that Au nanoparticles prepared with Na3C6H5O7 as a reductant were within the size of 10~20nm and prepared with NaBH4 as a reducing agent were within the size of 3~10nm. The optimum molar ratio of Na3C6H5O7 and HAuCl4 was 1.5:1. The gold nano-particles prepared after adding HAuCl4 to the hot Na3C6H5O7 mixed with Poly Vingl Pyrrolidone (PVP) solution are better dispersed, smaller size and more uniform than the goad nano-particles prepared after adding Na3C6H5O7 to the hot HAuCl4 mixed with PVP solution.the UV-visible absorption spectra analysis of Gold nano-particles prepared with Na3C6H5O7 as a reductant under high temperature and high pressure treatment. Generally speaking, gold nanoparticles changes little after high temperature and high pressure treantment, so the gold nanoparticles can be disinfected under high temperature and high pressure in cytotoxicity test.
The toxicity test with cell manifested that the Gold nano-particles within a certain concentration range could promote the proliferation of normal cell of Human Skin in a tim e-dependent and dose- dependent manner. Under the circumstance of below 50ηmol / L, the facilitation of Gold nano-particles towards cell proliferation strengthened as the density increased. At 50ηmol / L, the facilitation ability was most significant. However, the facilitation ability weakened as the density continuelly increased in the circumstance of above 50ηmol / L, and gradually converted to inhibition action. The activity of cancer cell showed invisible changes when the density of Gold nano-particles was below 50ηmol / L, and when the density is above 50ηmol / L, the inhibition action on cancer cell increased as the density increased. Stable emulsion can be obtained by adding the gold nanoparticles into the Cosmetics foundamental formula, which showed that the gold nanoparticles had no effect on the stablity of the emulsion.
通过化学还原法制备出不同粒径的纳米金颗粒,利用紫外可见分光光度计和透射电子显微镜对纳米金颗粒的形貌及尺寸进行表征。讨论了不同条件对纳米金制备的影响。结果表明, Na3C6H5O7为还原剂制得纳米金颗粒粒径在15-20nm之间,NaBH4为还原剂制得的纳米金颗粒粒径在3-10nm之间;柠檬酸钠与氯金酸的摩尔比为1.5:1时最佳;Na3C6H5O7为还原剂时,采用HAuCl4溶液加入到加热的Na3C6H5O7与聚乙烯吡咯烷酮(PVP)混合溶液比Na3C6H5O7溶液加入到加热的HAuCl4与PVP混合溶液制得的纳米金溶胶的颗粒分散性好,粒径小且更均一。粒径在15-20nm的纳米金经金高温高压处理其紫外可见吸收光谱分析,总体来说纳米金经高温高压处理变化很小,故细胞毒性试验过程中纳米金的灭菌可以使用高温高压的方法。
通过细胞毒性试验得:纳米金对人体皮肤正常细胞在一定浓度范围内均可促进细胞增殖,具有剂量依赖性和时间依赖性,在小于50ηmol/L时,随浓度的增加,其对细胞增殖的促进作用增加,在50ηmol/L时,对细胞增殖表现为最强的显著性促进作用,而后随浓度的增加,促进作用减弱,并逐步转化为对细胞增殖的抑制作用。纳米金对癌细胞作用,在浓度小于50ηmol/L时细胞活性均没有发生明显变化,在浓度大于50ηmol/L时,随浓度的增加,对细胞抑制作用增强。通过将纳米金加入到化妆品的基本配方中,制备出了稳定的乳状液,说明纳米金对乳状液的稳定性状不会产生影响。
The paper studied on the Synthesis and characterization of gold nanoparticles and the change of UV-visible absorption spectra under high temperature and high pressure treatment. And detect toxic effect of gold nanoparticles with diameter between 15nm and 20nm by MTT assay and 3H-TdR incorporation method. The purpose is to provide experimental evidence for gold nanoparticles applied in cosmetics. So choose normal cell of Human skin(human epidermal cell, Human hypertrophic scar derived fibroblasts also called HSF) and cancer cell(Hela, K562, CHO) were chosen as experi mental subjects.
Gold nano-particles with various diameters were prepared by chemical reduction, UV-Vis spectroscopy and transmission electron microscopy(TEM)were used to characterize the morphology and size of the prepared Au nanoparticles, The influence of the different syhthetic condition have been studied. The results show that Au nanoparticles prepared with Na3C6H5O7 as a reductant were within the size of 10~20nm and prepared with NaBH4 as a reducing agent were within the size of 3~10nm. The optimum molar ratio of Na3C6H5O7 and HAuCl4 was 1.5:1. The gold nano-particles prepared after adding HAuCl4 to the hot Na3C6H5O7 mixed with Poly Vingl Pyrrolidone (PVP) solution are better dispersed, smaller size and more uniform than the goad nano-particles prepared after adding Na3C6H5O7 to the hot HAuCl4 mixed with PVP solution.the UV-visible absorption spectra analysis of Gold nano-particles prepared with Na3C6H5O7 as a reductant under high temperature and high pressure treatment. Generally speaking, gold nanoparticles changes little after high temperature and high pressure treantment, so the gold nanoparticles can be disinfected under high temperature and high pressure in cytotoxicity test.
The toxicity test with cell manifested that the Gold nano-particles within a certain concentration range could promote the proliferation of normal cell of Human Skin in a tim e-dependent and dose- dependent manner. Under the circumstance of below 50ηmol / L, the facilitation of Gold nano-particles towards cell proliferation strengthened as the density increased. At 50ηmol / L, the facilitation ability was most significant. However, the facilitation ability weakened as the density continuelly increased in the circumstance of above 50ηmol / L, and gradually converted to inhibition action. The activity of cancer cell showed invisible changes when the density of Gold nano-particles was below 50ηmol / L, and when the density is above 50ηmol / L, the inhibition action on cancer cell increased as the density increased. Stable emulsion can be obtained by adding the gold nanoparticles into the Cosmetics foundamental formula, which showed that the gold nanoparticles had no effect on the stablity of the emulsion.
引文
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[3]陶泳,高滋.金的催化作用[J].化学世界,2005. 46(2):114-117
[4] Y K Du, P Yang, Z G Mou, et a1.Thermal decomposition behaviof of PVP coated on platinum nanoparticles[J].J Appl Polym Sci,2006,99(1):23—26.
[5] MC Daniel, D Astruc.Gold Nanoparticles: AssembIy,supmmolecular Chemistry, Quantum-Size-Related ProPerties, and Applications toward Biology, Catalysis, and Nanotechnol-ogy[J].chem Rev, 2004, 104(1):293-346.
[6]邓永沛,赵红秋等.纳米金颗粒在仿生工程中的应用[J].中国基础科学·科学前沿, 11-17. 2006, 29(4)
[7]任龙芳,强涛涛.纳米材料在化妆品中的应用王学川[J].日用化学品科学, 2006, 29(4): 15-18
[8]陈文革,段希萌.纳米化妆品及其研究进展[J].中国粉体技术, 2007, 6: 41-44
[9]裘炳毅.化妆品化学与工艺技术大全(上册)〔M〕.中国轻工业出版社,1997
[10]自景瑞,腾进.化妆品配方设计及应用实例[M].中川石化出版社. 2001
[11]肖子英,萧明.中国化妆品工业[J].日用化学品科学,2005,25(2): 9-11
[12]张殿义.现状与趋势[J].中国化妆品,2002,2: 40-43
[13]李群,纳米材料的制备与应用技术[M],北京:化学工业出版社,2008
[14]朱红.纳米材料化学及其应用[M].北京:清华大学出版社·北京交通大学出版社.2009.
[15]高志贤,李小强.纳米生物医药[M],化学工业出版社,北京,2007.
[16]张阳德.纳米生物分析化学与分子生物学,化学工业出版社[M],北京,2005.
[17]黄德欢.纳米技术与应用[M].上海:中国纺织大学出版社,2001.
[18]王世敏,许祖勋,傅晶.纳米材料制备技术[M],化学工业出版社,北京,2002
[19]张立德,纳米材料[M].北京:化学工业出版社,2000.
[20]谢娟,王延吉,李艳廷等.粒径可控纳米金的制备及表征[J].黄金,2008,29(7):3-6.
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