用于腫瘤治療的熱種子材料與金磁納米材料的制備與性能研究
發(fā)布時間：2018-12-12 06:55
【摘要】：Fe304為基礎(chǔ)的熱種子材料Fe3O4@CNTs (Fe3O4包覆CNTs)與金磁納米材料Au@Fe3O4 (Au包覆Fe3O4),均具有良好的生物穩(wěn)定性、生物相容性、無毒性和磁靶向特性,因此在腫瘤治療等生物醫(yī)學領(lǐng)域得到廣泛的應(yīng)用。其中,熱種子材料Fe3O4@CNTs主要應(yīng)用于腫瘤熱療,金磁納米材料Au@Fe304則在腫瘤化療中作為靶向藥物載體得以應(yīng)用。然而,應(yīng)用過程發(fā)現(xiàn),對熱種子材料Fe3O4@CNTs,碳納米管表面的Fe3O4的包覆情況及包覆完成后的分散情況,以及磁性納米顆粒所需的最適宜鐵碳比等問題,都會對腫瘤熱療產(chǎn)生重要影響；同樣,對金磁納米材料Au@Fe3O4, Fe3O4納米微球的成形性、Au納米粒子對Fe3O4表面包覆性能、以及粒子團聚和分散性不好等問題,也會嚴重影響其作為腫瘤化療中的靶向藥物載體的應(yīng)用。而且,由于金磁納米材料Au@Fe3O4本身不具有可供檢測的熒光性能,這就使該材料的應(yīng)用受到了一定程度的限制。因此,優(yōu)化兩種材料的制備技術(shù),探究可供示蹤檢測用的Au@Fe3O4生物材料是一項極具實用價值和挑戰(zhàn)性的工作。本文利用化學沉淀法制備了形貌均一、分散性良好、包覆均勻的熱種子材料Fe3O4@CNTs;利用聚乙二醇為分散劑,水熱法制備了尺寸適宜、成形良好、分散性良好的納米級Fe3O4微球；利用晶種生長法制備了包覆均勻、分散性良好的金磁納米材料Au@Fe3O4,并在此基礎(chǔ)上利用溶膠凝膠法制備得到Au@Fe3O4/YVO4:Yb3+,Er3+熒光納米粒子,為探究Au@Fe3O4在生物體內(nèi)的流轉(zhuǎn)和沉積提供了研究基礎(chǔ)和技術(shù)準備。通過XRD、TEM、SEM、FTIR和熒光分析等表征手段,研究了幾個影響因素對制備結(jié)果的影響,并對其物相組成、結(jié)晶性、微觀形貌和熒光性能進行了分析。本文的主要研究內(nèi)容及結(jié)果如下：(1)通過化學共沉淀法制備得到熱種子材料Fe3O4@CNTs,并分別探討了研究過程中加入不同質(zhì)量的碳納米管和不同種類的表面活性劑對樣品性能的影響。結(jié)果發(fā)現(xiàn),在相同的表面活性劑和相同的研究條件下,碳納米管含量為12.5%時,鐵氧體在碳納米管表面包覆的最好,最為均勻。在碳納米管含量均為12.5%和相同的研究條件下,十六烷基三甲基溴化銨(CTAB)作為表面活性劑制得樣品的性能要優(yōu)于十二烷基硫酸鈉(SDS)和壬基酚聚氧乙烯醚(IGO)作為表面活性劑制得的樣品。因此,最佳工藝參數(shù)為CNTs含量為12.5%,并選用CTAB為表面活性劑。此時,碳納米管的表面包覆均勻,磁飽和強度也達到了腫瘤靶向熱療的要求。(2)以聚乙二醇為分散劑,水熱法制備的Fe3O4為原料,利用晶種生長法制備得到金磁納米材料Au@Fe3O4,并探討了Fe3O4添加量,即鐵金比對樣品制備的影響。結(jié)果表明,以PEG200為分散劑,可以制備出粒徑為300-400nm左右,呈均勻球狀的Fe3O4納米顆粒；Fe3O4添加量過多、鐵金比過大時,納米Au顆粒太少而不足以完成包覆,會存在很多裸露的Fe3O4；而Fe3O4添加量過少、鐵金比過小時,納米Au顆粒太多,會在Fe3O4表面發(fā)生團聚,包覆不均勻；只有當Fe3O4添加量適中、鐵金比恰當時,納米Au顆粒才可以較為均勻地包覆在Fe3O4的表面。通過對比研究得出,最為適合的Fe3O4添加量為0.03g,即：Fe3O4:Au=3:8時可以滿足納米Au顆粒對Fe3O4納米微球的均勻包覆。(3)以硝酸鐿、硝酸鉺和釩酸釔為原料,檸檬酸為絡(luò)合劑,在溶膠凝膠法制備YVO4:Yb3+,Er3+熒光納米粒子過程中加入已制備好的Au@Fe3O4,制備得到Au@Fe3O4/YVO4:Yb3+,Er3+熒光納米粒子。SEMs XRD測試表明,在Au@Fe3O4的表面沉積YVO4:Yb3+,Er3+上轉(zhuǎn)換熒光納米粒子對金磁納米材料Au@Fe3O4的晶體結(jié)構(gòu)和穩(wěn)定性沒有影響；而且,Au@Fe3O4/YVO4:Yb3+,Er3+樣品在980nm激光激發(fā)下,會發(fā)射出明顯的綠色熒光。總之,本文成功制備了熒光納米粒子Au@Fe3O/YVO4:Yb3+,Er3+,為后續(xù)實現(xiàn)金磁納米材料Au@Fe3O4在動物體內(nèi)的示蹤提供了材料基礎(chǔ)。
[Abstract]:The Fe-304-based thermal seed material Fe3O4@CNTs (Fe3O4-coated CNTs) and the gold-magnetic nano-material Au@Fe3O4 (Au-coated Fe3O4) have good biological stability, biocompatibility, non-toxicity and magnetic targeting characteristics, and are widely used in the fields of biomedicine such as tumor treatment and the like. The Fe3O4@CNTs of the thermal seed material is mainly used for tumor thermal therapy, and the Au@Fe304 of the gold magnetic nano-material is used as a target drug carrier in the tumor chemotherapy. however, in that application process, the problem of the Fe3O4@CNTs of the hot seed material, the coating condition of Fe3O4 on the surface of the carbon nano tube and the dispersion condition after the coating are completed, as well as the most suitable iron-to-carbon ratio required by the magnetic nano-particles, can have an important effect on the heat treatment of the tumor, The Au@Fe3O4 of the gold-magnetic nano-material, the forming property of the Fe3O4 nano-ball, the coating performance of the Au nano-particles on the surface of the Fe3O4, the agglomeration and the poor dispersibility of the particles and the like can also be seriously affected as the application of the targeting drug carrier in the tumor chemotherapy. Moreover, since the gold magnetic nano-material Au@Fe3O4 itself does not have the fluorescence property that can be used for detection, the application of the material is limited to a certain degree. Therefore, to optimize the preparation technology of two materials, it is a practical and challenging work to explore the Au@Fe3O4 biological material that can be used for trace detection. The chemical precipitation method is used to prepare the hot seed material Fe3O4@CNTs with uniform morphology, good dispersibility and uniform coating, and the nano-scale Fe3O4 micro-spheres with proper size, good shape and good dispersivity are prepared by using the polyethylene glycol as the dispersing agent and the water heat method. The gold magnetic nano-material Au @ Fe3O4 with uniform and good dispersibility is prepared by the crystal seed growing method, and the Au @ Fe3O4/ YVO4: Yb3 +, Er3 + fluorescent nano-particles are prepared by the sol-gel method. In order to study the flow and deposition of the Au@Fe3O4 in the living body, the research foundation and the technical preparation are provided. The influence of several factors on the preparation results was studied by means of XRD, TEM, SEM, FTIR and fluorescence analysis. The main contents and results of this paper are as follows: (1) The Fe3O4@CNTs of the hot seed material is obtained by the chemical co-precipitation method, and the effect of different quality carbon nanotubes and different kinds of surfactant on the performance of the sample is also discussed. The results show that, under the same surface active agent and the same research condition, the content of the carbon nano-tube is 12.5%, the best and the most uniform of the ferrite on the surface of the carbon nano-tube. The performance of CTAB as a surfactant was superior to that of sodium dodecyl sulfate (SDS) and nonylphenol polyoxyethylene ether (IGO) as a surfactant under the same study conditions. Therefore, the optimum process parameters were CNs content of 12.5% and CTAB as the surface active agent. At this time, the surface of the carbon nanotube is uniformly coated, and the magnetic saturation intensity also reaches the requirement of the tumor targeted thermal therapy. (2) The Au@Fe3O4 of the gold-magnetic nano-material was prepared by using the Fe3O4 as the dispersing agent and the hydrothermal method, and the effect of the addition amount of the Fe3O4, that is, the iron-to-gold ratio on the preparation of the sample, was also discussed. The results show that the nano-Au particles with the particle size of 300-400nm can be prepared by using the PEG200 as the dispersing agent, and the Fe3O4 nano-particles with uniform spherical shape can be prepared; the addition amount of the Fe3O4 is too large; when the iron-to-gold ratio is too large, the nano-Au particles are too small to complete the coating, so that a plurality of bare Fe3O4 is present; and the addition amount of the Fe3O4 is too small, When the iron-gold ratio is more than an hour, the nano-Au particles are too large to be agglomerated on the surface of the Fe3O4, and the coating is not uniform; only when the addition amount of the Fe3O4 is moderate and the iron-gold ratio is appropriate, the nano-Au particles can be more uniformly coated on the surface of the Fe3O4. The results show that the most suitable Fe _ 3O _ 4 is 0. 03g, that is, Fe3O4: Au = 3: 8, which can satisfy the uniform coating of the nano-Au particles on the Fe3O4 nano-spheres. and (3) adding the prepared Au@Fe3O4 into the process of preparing the YVO4: Yb3 +, Er3 + fluorescent nano-particles by using the nitric acid solution, the nitric acid salt and the ferroic acid as the raw material and the citric acid as a complexing agent, and preparing the Au@Fe3O4/ YVO4: Yb3 +, Er3 + fluorescent nano-particles. The SEMS XRD test shows that the conversion of the fluorescent nanoparticles on the surface of the Au@Fe3O4 has no effect on the crystal structure and the stability of the Au@Fe3O4 of the gold-magnetic nano-material; moreover, the Au@Fe3O4/ YVO4: Yb3 + and Er3 + samples are excited by a 980nm laser, a clear green fluorescence is emitted. In conclusion, the Au@Fe3O/ YVO4: Yb3 + and Er3 + of the fluorescent nano-particles were successfully prepared in this paper, which provided a material basis for the follow-up of the Au@Fe3O4 of the gold-magnetic nano-material.
【學位授予單位】：山東大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：TB383.1
本文編號：2374136
[Abstract]:The Fe-304-based thermal seed material Fe3O4@CNTs (Fe3O4-coated CNTs) and the gold-magnetic nano-material Au@Fe3O4 (Au-coated Fe3O4) have good biological stability, biocompatibility, non-toxicity and magnetic targeting characteristics, and are widely used in the fields of biomedicine such as tumor treatment and the like. The Fe3O4@CNTs of the thermal seed material is mainly used for tumor thermal therapy, and the Au@Fe304 of the gold magnetic nano-material is used as a target drug carrier in the tumor chemotherapy. however, in that application process, the problem of the Fe3O4@CNTs of the hot seed material, the coating condition of Fe3O4 on the surface of the carbon nano tube and the dispersion condition after the coating are completed, as well as the most suitable iron-to-carbon ratio required by the magnetic nano-particles, can have an important effect on the heat treatment of the tumor, The Au@Fe3O4 of the gold-magnetic nano-material, the forming property of the Fe3O4 nano-ball, the coating performance of the Au nano-particles on the surface of the Fe3O4, the agglomeration and the poor dispersibility of the particles and the like can also be seriously affected as the application of the targeting drug carrier in the tumor chemotherapy. Moreover, since the gold magnetic nano-material Au@Fe3O4 itself does not have the fluorescence property that can be used for detection, the application of the material is limited to a certain degree. Therefore, to optimize the preparation technology of two materials, it is a practical and challenging work to explore the Au@Fe3O4 biological material that can be used for trace detection. The chemical precipitation method is used to prepare the hot seed material Fe3O4@CNTs with uniform morphology, good dispersibility and uniform coating, and the nano-scale Fe3O4 micro-spheres with proper size, good shape and good dispersivity are prepared by using the polyethylene glycol as the dispersing agent and the water heat method. The gold magnetic nano-material Au @ Fe3O4 with uniform and good dispersibility is prepared by the crystal seed growing method, and the Au @ Fe3O4/ YVO4: Yb3 +, Er3 + fluorescent nano-particles are prepared by the sol-gel method. In order to study the flow and deposition of the Au@Fe3O4 in the living body, the research foundation and the technical preparation are provided. The influence of several factors on the preparation results was studied by means of XRD, TEM, SEM, FTIR and fluorescence analysis. The main contents and results of this paper are as follows: (1) The Fe3O4@CNTs of the hot seed material is obtained by the chemical co-precipitation method, and the effect of different quality carbon nanotubes and different kinds of surfactant on the performance of the sample is also discussed. The results show that, under the same surface active agent and the same research condition, the content of the carbon nano-tube is 12.5%, the best and the most uniform of the ferrite on the surface of the carbon nano-tube. The performance of CTAB as a surfactant was superior to that of sodium dodecyl sulfate (SDS) and nonylphenol polyoxyethylene ether (IGO) as a surfactant under the same study conditions. Therefore, the optimum process parameters were CNs content of 12.5% and CTAB as the surface active agent. At this time, the surface of the carbon nanotube is uniformly coated, and the magnetic saturation intensity also reaches the requirement of the tumor targeted thermal therapy. (2) The Au@Fe3O4 of the gold-magnetic nano-material was prepared by using the Fe3O4 as the dispersing agent and the hydrothermal method, and the effect of the addition amount of the Fe3O4, that is, the iron-to-gold ratio on the preparation of the sample, was also discussed. The results show that the nano-Au particles with the particle size of 300-400nm can be prepared by using the PEG200 as the dispersing agent, and the Fe3O4 nano-particles with uniform spherical shape can be prepared; the addition amount of the Fe3O4 is too large; when the iron-to-gold ratio is too large, the nano-Au particles are too small to complete the coating, so that a plurality of bare Fe3O4 is present; and the addition amount of the Fe3O4 is too small, When the iron-gold ratio is more than an hour, the nano-Au particles are too large to be agglomerated on the surface of the Fe3O4, and the coating is not uniform; only when the addition amount of the Fe3O4 is moderate and the iron-gold ratio is appropriate, the nano-Au particles can be more uniformly coated on the surface of the Fe3O4. The results show that the most suitable Fe _ 3O _ 4 is 0. 03g, that is, Fe3O4: Au = 3: 8, which can satisfy the uniform coating of the nano-Au particles on the Fe3O4 nano-spheres. and (3) adding the prepared Au@Fe3O4 into the process of preparing the YVO4: Yb3 +, Er3 + fluorescent nano-particles by using the nitric acid solution, the nitric acid salt and the ferroic acid as the raw material and the citric acid as a complexing agent, and preparing the Au@Fe3O4/ YVO4: Yb3 +, Er3 + fluorescent nano-particles. The SEMS XRD test shows that the conversion of the fluorescent nanoparticles on the surface of the Au@Fe3O4 has no effect on the crystal structure and the stability of the Au@Fe3O4 of the gold-magnetic nano-material; moreover, the Au@Fe3O4/ YVO4: Yb3 + and Er3 + samples are excited by a 980nm laser, a clear green fluorescence is emitted. In conclusion, the Au@Fe3O/ YVO4: Yb3 + and Er3 + of the fluorescent nano-particles were successfully prepared in this paper, which provided a material basis for the follow-up of the Au@Fe3O4 of the gold-magnetic nano-material.
【學位授予單位】：山東大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：TB383.1
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