Fe_3O_4/CA@CQDs磁性荧光复合材料的制备及表征
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摘要
为了制备出低毒且性能优异的磁性荧光复合材料,选用发光稳定且生物相容性高的碳量子点(CQDs)作为荧光探针,分别采用一步水热法和化学共沉淀法制备了荧光性能优异的CQDs和超顺磁性四氧化三铁(Fe_3O_4),再以生物相容性较好的柠檬酸(CA)修饰Fe_3O_4,得到表面富含功能性羟基和羧基的Fe_3O_4/CA,通过偶联剂乙二胺将CQDs与Fe_3O_4/CA连接,成功制得Fe_3O_4/CA@CQDs磁性荧光复合材料。并对其进行红外光谱(FTIR)、荧光光谱、振动样品磁强计(VSM)、X射线衍射仪(XRD)、荧光显微镜及透射电子显微镜(TEM)表征,结果表明:Fe_3O_4/CA@CQDs为核壳结构,粒径为30～40 nm,饱和磁化强度为20.14 A·m~2·kg~(-1),该双功能复合材料具有优良的荧光性能和磁性能,细胞毒性低且生物相容性高,有望取代传统荧光磁性纳米复合材料,并广泛应用于生物医学领域。
For preparation of low toxicity and excellent magnetic-fluorescent composite material, carbon quantum dots(CQDs) with high light stability and biocompatibility were selected as fluorescent probe. The CQDs with excellent fluorescence were successfully synthesized by one-step hydrothermal method. Superparamagnetic nanoparticles Fe_3O_4 were prepared by hydrothermal coprecipitation, which were modified by citric acid(CA) with good biocompatibility.Then Fe_3O_4/CA was formed and riched of functional hydroxyl and carboxylgroups. Through coupling agent ethylenediamine, the CQDs were connected with Fe_3O_4/CA for successful preparation of magnetic-fluorescent composite material Fe_3O_4/CA@CQDs. Fourier transform infrared spectroscopy(FTIR), fluorescence spectrophotometer, vibrating sample magnetometer(VSM), X-ray diffraction(XRD), fluorescence microscope and transmission electron microscopy(TEM) were used for characterization. The results show that the Fe_3O_4/CA@CQDs possessed core shell structure with an average diameter of 30-40 nm and the saturation magnetic intensity 20.14 A·m~2·kg~(-1). Attributed to the excellent fluorescence properties and magnetic, low cytotoxicity and high biocompatibility, the bifunction composite material is expected to replace traditional magnetic-fluorescent nanocomposites and widely used in biomedical fields.
For preparation of low toxicity and excellent magnetic-fluorescent composite material, carbon quantum dots(CQDs) with high light stability and biocompatibility were selected as fluorescent probe. The CQDs with excellent fluorescence were successfully synthesized by one-step hydrothermal method. Superparamagnetic nanoparticles Fe_3O_4 were prepared by hydrothermal coprecipitation, which were modified by citric acid(CA) with good biocompatibility.Then Fe_3O_4/CA was formed and riched of functional hydroxyl and carboxylgroups. Through coupling agent ethylenediamine, the CQDs were connected with Fe_3O_4/CA for successful preparation of magnetic-fluorescent composite material Fe_3O_4/CA@CQDs. Fourier transform infrared spectroscopy(FTIR), fluorescence spectrophotometer, vibrating sample magnetometer(VSM), X-ray diffraction(XRD), fluorescence microscope and transmission electron microscopy(TEM) were used for characterization. The results show that the Fe_3O_4/CA@CQDs possessed core shell structure with an average diameter of 30-40 nm and the saturation magnetic intensity 20.14 A·m~2·kg~(-1). Attributed to the excellent fluorescence properties and magnetic, low cytotoxicity and high biocompatibility, the bifunction composite material is expected to replace traditional magnetic-fluorescent nanocomposites and widely used in biomedical fields.
引文
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[2] ARRIORTUA O K,GARAIO E,HERRERO DE LA PARTE B,et al..Antitumor magnetic hyperthermia induced by RGD-functionalized Fe3O4nanoparticles,in an experimental model of colorectal liver metastases [J].Beilstein.J.Nanotechnol.,2016,7:1532-1542.
[3] ZHANG Z,GUAN Y P,XIA T T,et al..Influence of exposed magnetic nanoparticles and their application in chemiluminescence immunoassay [J].Colloids Surf.A Phys.Eng.Aspects,2017,520:335-342.
[4] REDDY P M,CHANG K C,LIU Z J,et al..Functionalized magnetic iron oxide (Fe3O4) nanoparticles for capturing gram-positive and gram-negative bacteria [J].J.Biomed.Nanotechnol.,2014,10(8):1429-1439.
[5] KARAMIPOUR S H,SADJADI M S,FARHADYAR N.Fabrication and spectroscopic studies of folic acid-conjugated Fe3O4@Au core-shell for targeted drug delivery application [J].Spectrochim.Acta Part A Mol.Biomol.Spectrosc.,2015,148:146-155.
[6] GARCíAR S,STAFFORDS,GUN'KO Y K.Recent progress in synthesis and functionalization of multimodal fluorescent-magnetic nanoparticles for biological applications [J].Appl.Sci.,2018,8(2):172-1-23.
[7] KYEONG S,JEONG C,HAN Y K,et al..Fabrication of mono-dispersed silica-coated quantum dot-assembled magnetic nanoparticles [J].RSC Adv.,2015,5(41):32072-32077.
[8] DING Y L,YIN H,SHEN S,et al..Chitosan-based magnetic/fluorescent nanocomposites for cell labelling and controlled drug release [J].New J.Chem.,2017,41(4):1736-1743.
[9] ZHOU L L,ZHANG X Y,LIU L,et al..Multifunctional fluorescent magnetic nanoparticles:synthesis,characterization and targeted cell imaging applications [J].Chin.J.Chem.,2017,35(6):977-983.
[10] 莫尊理,蒋彩弟,蒲斌,等.基于Fe3O4纳米粒子的磁性荧光复合材料研究进展 [J].材料导报,2013,27(8):42-45.MO Z L,JIANG C D,PU B,et al..Research progress on magnetic-fluorescent Fe3O4-based nanocomposites [J].Mater.Rev.,2013,27(8):42-45.(in Chinese)
[11] CHEKINA N,HORAK D,JENDELOVA P,et al..Fluorescent magnetic nanoparticles for biomedical applications [J].J.Mater.Chem.,2011,21(2):7630-7639.
[12] LU Y J,HE B C,SHEN J,et al..Multifunctional magnetic and fluorescent core-shell nanoparticles for bioimaging [J].Nanoscale,2015,7(5):1606-1609.
[13] KOC K,KARAKUS B,RAJAR K,et al..Synthesis and characterization of ZnS@Fe3O4 fluorescent-magnetic bifunctional nanospheres [J].Superlattices Microstruct.,2017,110:198-204.
[14] 黄艳凤,孙晓毅,陈玉烨,等.Fe3O4-CdTe/CdS磁性荧光复合材料的制备 [J].现代化工,2018,38(1):76-79.HUANG Y F,SUN X Y,CHEN Y Y,et al..Preparation of Fe3O4-CdTe/CdS magnetic fluorescent composites [J].Mod.Chem.Ind.,2018,38(1):76-79.(in Chinese)
[15] 周翔,王秀玲,刘勇健,等.Fe3O4/PEI/Au@CdSe/CdS多功能复合材料的制备与表征 [J].无机化学学报,2015,31(6):1165-1170 ZHOU X,WANG X L,LIU Y J,et al..Preparation and characterization of Fe3O4/PEI/Au@CdSe/CdS multifunctional composite materials [J].Chin.J.Inorg.Chem.,2015,31(6):1165-1170.(in Chinese)
[16] ZHOU S,CHEN Q W,HU X Y,et al..Bifunctional luminescent superparamagnetic nanocomposites of CdSe/CdS-Fe3O4 synthesized via a facile method [J].J.Mater.Chem.,2012,22(17):8263-8270.
[17] TU D,LIU Y S,ZHU H M,et al..Optical/magnetic multimodal bioprobes based on lanthanide-doped inorganic nanocrystals [J].Chem.-A Eur.J.,2013,19(18):5516-5527.
[18] ESCUDERO A,BECERRO A I,CARRILLO-CARRIóN C,et al..Rare earth based nanostructured materials:synthesis,functionalization,properties andbioimaging and biosensing applications [J].Nanophotonics,2017,6(5):881-921.
[19] XU X Y,RAY R,GU Y L,et al..Electrophoretic analysis and purification of fluorescent single-walled carbon nanotube fragments [J].J.Am.Chem.Soc.,2004,126(40):12736-12737.
[20] XIAO Y Y,LIU L,CHEN Y,et al..Developmental toxicity of carbon quantum dots to the embryos/larvae of rare minnow (Gobiocypris rarus) [J].Biomed Res.Int.,2016,2016:4016402-1-11.
[21] LI Q,OHULCHANSKYY T Y,LIU R L,et al..Photoluminescent carbon dots as biocompatible nanoprobes for targeting cancer cells in vitro [J].J.Phys.Chem.C,2010,114(28):12062-12068.
[22] WANG Y F,HU A G.Carbon quantum dots:synthesis,properties and applications [J].J.Mater.Chem.C,2014,2(24):6921-6939.
[23] LI S Z,ZHOU S H,XU H B,et al..Luminescent properties and sensing performance of a carbon quantum dot encapsulated mesoporous silica/polyacrylonitrile electrospun nanofibrous membrane [J].J.Mater.Sci.,2016,51(14):6801-6811.
[24] 田瑞雪,武玲玲,赵清,等.碳量子点的氨基化及其对发光性能的影响 [J].化工新型材料,2014,42(1):90-92.TIAN R X,WU L L,ZHAO Q,et al..Preparation and photoluminescence property of amine-containing carbon quantum dots [J].New Chem.Mater.,2014,42(1):90-92.(in Chinese)
[25] 陈亭汝,孙瑾.Fe3O4磁性纳米粒子的共沉淀法制备研究 [J].应用化工,2009,38(2):226-228.CHEN T R,SUN J.Study on preparation of magnetic Fe3O4 nano-particles with liquid-state co-precipitation method [J].Appl.Chem.Ind.,2009,38(2):226-228.(in Chinese)
[26] 王莉,吕婷,阮枫萍,等.水热法制备的荧光碳量子点 [J].发光学报,2014,35(6):706-709.WANG L,LYU T,RUAN F P,et al..Synthesis of photoluminescent carbon nanoparticles by hydrothermal method [J].Chin.J.Lumin.,2014,35(6):706-709.(in Chinese)