Fe_3O_4纳米粒子的可控制备及其表面改性
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摘要
四氧化三铁(Fe_3O_4)因在细胞分离、靶向药物、磁共振成像等生物医学领域具有广阔的应用前景而成为研究热点。本文采用溶剂热法合成了Fe_3O_4纳米粒子,并详细研究了反应温度、反应时间和反应前驱体组成对Fe_3O_4结构和形貌的影响。实验结果表明,反应时间对球形纳米颗粒的尺寸影响不大,反应时间为12 h时,球的直径达到了最大,继续延长反应时间,球的尺寸保持不变;200℃容易生成大尺寸的Fe_3O_4纳米粒子;反应物的组成对Fe_3O_4纳米粒子的形貌也有一定的影响,当用水合肼代替乙二胺时,得到的是立方体形状的Fe_3O_4。为了增加Fe_3O_4纳米粒子的化学稳定性、生物相容性和作为药物载体的可能性,我们用St?ber方法在Fe_3O_4纳米粒子的表面包覆了一层SiO_2介孔分子筛,并探索了超声和机械搅拌对核壳结构形貌的影响,还研究了包覆前后样品的磁学性质。
Fe_3O_4 has a wide application prospect in biomedical fields such as cell separation, targeted drugs, magnetic resonance imaging and so on. In this work, Fe_3O_4 nanoparticles were synthesized by solvothermal method, and the effects of reaction temperature, reaction time and precursor composition on the structure and morphology of Fe_3O_4 were studied in detail. The reaction time had little effect on the size of the spherical nanoparticles. When the reaction time was 12 h, the diameter of the spheres reached the maximum. When the reaction time was increased, the size of the spheres kept constant. The reaction did not occur when the reaction temperature was 120 ℃. Face-centered cubic structure Fe_3O_4 was obtained when the reaction temperature was 160, 200, 240 ℃. The diameter of Fe_3O_4 was maximum when the reaction temperature was 200 ℃. Cube-shaped Fe_3O_4 was obtained when ethylenediamine was replaced by hydrazine hydrate. In order to improve the chemical stability, biocompatibility and the possibility using Fe_3O_4 nanoparticles as drug carriers, a layer of SiO_2 mesoporous molecular sieve was coated on the surface of Fe_3O_4 by St?ber method. The effects of ultrasonic and mechanical stirring on the morphology of core-shell structure were investigated. The magnetic properties of the samples before and after SiO_2 coating were also studied. The samples were all superparamagnetic before and after coating.
Fe_3O_4 has a wide application prospect in biomedical fields such as cell separation, targeted drugs, magnetic resonance imaging and so on. In this work, Fe_3O_4 nanoparticles were synthesized by solvothermal method, and the effects of reaction temperature, reaction time and precursor composition on the structure and morphology of Fe_3O_4 were studied in detail. The reaction time had little effect on the size of the spherical nanoparticles. When the reaction time was 12 h, the diameter of the spheres reached the maximum. When the reaction time was increased, the size of the spheres kept constant. The reaction did not occur when the reaction temperature was 120 ℃. Face-centered cubic structure Fe_3O_4 was obtained when the reaction temperature was 160, 200, 240 ℃. The diameter of Fe_3O_4 was maximum when the reaction temperature was 200 ℃. Cube-shaped Fe_3O_4 was obtained when ethylenediamine was replaced by hydrazine hydrate. In order to improve the chemical stability, biocompatibility and the possibility using Fe_3O_4 nanoparticles as drug carriers, a layer of SiO_2 mesoporous molecular sieve was coated on the surface of Fe_3O_4 by St?ber method. The effects of ultrasonic and mechanical stirring on the morphology of core-shell structure were investigated. The magnetic properties of the samples before and after SiO_2 coating were also studied. The samples were all superparamagnetic before and after coating.
引文
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[19] XU X,DENG C,GAO M,et al..Synthesis of magnetic microspheres with immobilized metal ions forenrichment and direct determination of phosphopeptides bymatrix-assisted laser desorption ionization mass spectrometry [J].Adv.Mater.,2006,18(24):3289-3293.
[2] CHIKAZUMI S,TAKETOMI S,UKITA M,et al..Physics of magnetic fluids [J].J.Magn.Magn.Mater.,1987,65(2-3):245-251.
[3] LU A H,SCHMIDT W,MATOUSSEVITCH N,et al..Nanoengineering of a magnetically separable hydrogenation catalyst [J].Angew.Chem.,2004,116(33):4403-4406.
[4] MA P A,XIAO H H,YU C,et al..Enhanced cisplatin chemotherapy by iron oxide nanocarrier-mediated generation of highly toxic reactive oxygen species [J].Nano Lett.,2017,17(2):928-937.
[5] GE R,LI X,LIN M,et al..Fe3O4@polydopamine composite theranostic superparticles employing preassembled Fe3O4 nanoparticles as the core [J].ACS Appl.Mater.Interfaces,2016,8(35):22942-22952.
[6] YANG Y X,LIU Y C,CHENG C,et al..Rational design of GO-modified Fe3O4/SiO2 nanoparticles with combined rhenium-188 and gambogic acid for magnetic target therapy [J].ACS Appl.Mater.Interfaces,2017,9(34):28195-28208.
[7] DU S W,ZHANG L K,HAN K B,et al..Combined phycocyanin and hematoporphyrin monomethyl ether for breast cancer treatment via photosensitizers modified Fe3O4 nanoparticles inhibiting the proliferation and migration of MCF-7 cells [J].Biomacromolecules,2018,19(1):31-41.
[8] WANG W W,HAO C L,SUN M Z,et al..Spiky Fe3O4@Au supraparticles for multimodal in vivo imaging [J].Adv.Funct.Mater.,2018,28(22):1800310-1-8.
[9] LI Y,DING M J,WANG S,et al..Preparation of imprinted polymers at surface of magneticnanoparticles for the selective extraction of tadalafil from medicines [J].ACS Appl.Mater.Interfaces,2011,3(9):3308-3315.
[10] YANG C H,DU J J,PENG Q,et al..Polyaniline/Fe3O4 nanoparticle composite:synthesis and reaction mechanism [J].J.Phys.Chem.B,2009,113(15):5052-5058.
[11] TONG L Z,SHI J H,LIU D M,et al..Luminescent and magnetic properties of Fe3O4@SiO2@Y2O3∶Eu3+composites with core-shell structure [J].J.Phys.Chem.C,2012,116(12):7153-7157.
[12] 沈茂,陈素清,贾文平,等.Ag@Fe3O4@C-CdTe@SiO2磁性荧光复合微球的制备与光学特征 [J].发光学报,2017,38(3):274-280.SHEN M,CHEN S Q,JIA W P,et al..Magnetic and optical properties of Ag@Fe3O4@C-CdTe@SiO2 hybrid nanoparticles [J].Chin.J.Lumin.,2017,38(3):274-280.(in English)
[13] 刘江美,刘文涵,腾渊洁,等.2-噻吩甲酸在Fe3O4@Ag基底上的吸附及表面增强拉曼光谱 [J].发光学报,2015,36(12):1477-1484.LIU J M,LIU W H,TENG Y J,et al..Adsorption behavior of 2-thiophene carboxylic acid on Fe3O4@Ag substrate investigated by surface-enhanced Raman scattering [J].Chin.J.Lumin.,2015,36(12):1477-1484.(in Chinese)
[14] 高倩,张吉林,洪广言,等.不同形貌的Fe3O4微-纳米粒子的溶剂热合成 [J].高等学校化学学报,2011,32(3):552-559.GAO Q,ZHANG J L,HONG G Y,et al..Solvothermal synthesis of the magnetite micro-nano particles (Fe3O4) with different morphologies [J].Chem.J.Chin.Univ.,2011,32(3):552-559.(in Chinese)
[15] GUO S J,LI D,ZHANG L X,et al..Monodisperse mesoporous superparamagnetic single-crystal magnetite nanoparticles for drug delivery [J].Biomaterials,2009,30(10):1881-1889.
[16] SUN X K,DONG B,XU H W,et al..Amphiphilic silane modified multifunctional nanoparticles for magnetically targeted photodynamic therapy [J].ACS Appl.Mater.Interfaces,2017,9(13):11451-11460.
[17] ZHANG Y H,SU Z S,LI B,et al..Recyclable magnetic mesoporous nanocomposite with improved sensing performance toward nitrite [J].ACS Appl.Mater.Interfaces,2016,8(19):12344-12351.
[18] GE J P,HU Y X,BIASINI M,et al..Superparamagnetic magnetite colloidal nanocrystal clusters [J].Angew.Chem.Int.Ed.,2007,46(23):4342-4345.
[19] XU X,DENG C,GAO M,et al..Synthesis of magnetic microspheres with immobilized metal ions forenrichment and direct determination of phosphopeptides bymatrix-assisted laser desorption ionization mass spectrometry [J].Adv.Mater.,2006,18(24):3289-3293.
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