CN109399727B - 含金属原子簇的磁性氧化铁纳米颗粒及其制备和应用 - Google Patents
含金属原子簇的磁性氧化铁纳米颗粒及其制备和应用 Download PDFInfo
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- CN109399727B CN109399727B CN201811316448.9A CN201811316448A CN109399727B CN 109399727 B CN109399727 B CN 109399727B CN 201811316448 A CN201811316448 A CN 201811316448A CN 109399727 B CN109399727 B CN 109399727B
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- iron
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Abstract
本发明提供一种含金属原子簇的磁性氧化铁纳米颗粒,所述金属原子簇嵌合在氧化铁晶体基质中,且所述金属原子簇的含量占比为0.1‑15%。本发明还提供了上述含金属原子簇的磁性氧化铁纳米颗粒的制备方法,将氧化铁的金属前驱体、有机酸、有机胺按照比例溶于有机溶剂中形成均匀的反应体系,然后将所述反应体系在惰性气体氛围内加热到150‑350℃后,加入金属原子簇前驱体,升温回流反应至前驱体全部分解即可。本发明的纳米颗粒由于金属原子簇的嵌合使得磁性氧化铁颗粒的磁学性质得到提高,而氧化铁又充分保证了纳米颗粒性质的稳定性,因而能够更好的应用于生物医学检测与治疗等领域。
Description
技术领域
本发明涉及磁性氧化铁技术领域,具体涉及一种含金属原子簇的磁性氧化铁纳米颗粒及其制备和应用。
背景技术
近年来,磁性纳米颗粒的研究在各个学科领域都引起了人们的广泛兴趣,其中氧化铁作为一种重要的磁性材料,具有很好的生物相容性,除了在磁流体、催化剂和磁记录材料方面的应用,在生物分离、检测、靶向药物和医学成像方面也具有广泛的用途,已经在临床前或临床上被用于补铁剂(如ferumoxytol),磁共振成像造影剂(如),磁热疗剂(如欧洲监管批准的)以及药物载体。为了制备具有良好的生物学相容性、磁学性质优良且稳定磁性氧化铁纳米颗粒,美国专利号6,262,129,中国发明专利CN200580040484.1发明专利CN200480044382.2发明专利CN02820174.4以及Alivisatos课题组发表的J.Am.Chem.Soc.,1999,121(49),11595;Sun课题组发表的J.Am.Chem.Soc.,2002,124,8204;J.Am.Chem.Soc.,2004,126(1),273;Hyeon课题组发表的J.Am.Chem.Soc.,2001,123(51),12798;Nat.Mater.,2004,3(12),891;Peng,X.Chem.Mater.,2004,16,393等文件中都公开了利用高温热解法,制备均匀铁氧体、铁氧化物及铁及其合金等磁性纳米颗粒的方法。
虽然通过以上方法制备的磁性氧化铁颗粒具有均一尺寸、形貌和稳定的超顺磁学性质,然而这些磁性纳米颗粒在磁共振成像、细胞跟踪以及磁热转换效率中存在磁场响应低,成像灵敏度不足,磁热转换效率低性能等问题。因此如何提高氧化铁纳米颗粒的稳定性和磁学性能依然是目前磁性纳米材料研究的热点之一。常见的提高磁性氧化铁纳米颗粒的磁学性质的方法包括:制备尖晶石型结构结构的铁氧体纳米颗粒;制备立方形状的铁氧体纳米颗粒;或者形成具有交换耦合作用的铁氧体核/壳纳米结构等策略。然而,这些方法制备的颗粒均有一些不足,比如:铁氧体或者立方形貌对磁学性质和相应的应用性能提高有限;而对于铁氧体核/壳纳米结构,由于其制备过程复杂,使得反应过程不易控制。
发明内容
为了满足生物医学应用对高饱和磁化强度且性质稳定磁性氧化铁纳米颗粒的需求,本发明提供了一种含金属原子簇的磁性氧化铁纳米颗粒及其制备和应用。
为达到上述目的,本发明的技术方案如下:
含金属原子簇的磁性氧化铁纳米颗粒,所述金属原子簇嵌合在氧化铁晶体基质中,且所述金属原子簇在含金属原子簇的磁性氧化铁纳米颗粒中的含量占比为0.1-15%。
其中,所述金属原子簇的粒径大小为0.2-5nm,所述氧化铁晶体基质的粒径范围为2-100 nm。
优选地,所述氧化铁纳米颗粒粒径范围为3-50nm。
优选地,所述金属原子簇是由金属原子M形成的Mx原子簇,x的范围为3-100,所述M为稀土金属、第四周期过渡金属和后过渡金属中的一种或两种。
更优选地,所述M为Fe、Co、Ni、Mn、Ga、Nd、Sm、Tb、Dy、Ho、Er、Tm、Yb、 Ce中的一种或多种。
本发明提供的含金属原子簇的磁性氧化铁纳米颗粒,由于金属原子簇与氧化铁基质的相互作用,使得磁性纳米颗粒不仅具有生物相容性好,性质稳定的优点,而且进一步提高了饱和磁化强度。
为了实现上述目的,本发明还提供了含金属原子簇的磁性氧化铁纳米颗粒的制备方法,其特征在于,包括以下步骤:
S1、将氧化铁的金属前驱体、有机酸、有机胺按照比例溶于有机溶剂中形成均匀的反应体系;
S2、将S1中所述反应体系在惰性气体氛围内加热到150-350℃后,加入金属原子簇前驱体,升温回流反应至前驱体全部分解,即得到含金属原子簇的磁性纳米颗粒。
其中,所述金属前驱体为含铁有机配合物,所述金属原子簇前驱体为金属有机配合物;所述含铁有机配合物包括:芥酸铁、乙酰丙酮铁Fe(acac)3、油酸铁Fe(OA)3、五羰基合铁 Fe(CO)5、亚硝基羟基苯胺合铁FeCup3;所述金属有机配合物包括:乙酰丙酮铁Fe(acac)3、油酸铁Fe(OA)3、五羰基合铁Fe(CO)5、亚硝基羟基苯胺合铁FeCup3、Co2(CO)8、Co(acac)2、 Ni(OOCCH3)2、Ni(acac)2、油酸稀土配合物、乙酰丙酮稀土配合物。
其中,所述有机酸与有机胺的摩尔比为1:0.5-10,所述有机酸与有机溶剂的体积比为 1:1-100,所述有机胺与有机溶剂的体积比为1:1-100,所述金属前驱体的浓度为0.01-1mol/L。
优选地,所述有机酸为碳链长度介于6-25之间的有机酸,所述有机胺为碳链长度介于 6-25之间的有机胺,所述有机溶剂为还原性溶剂。
更优选地,所述有机酸为油酸、硬脂酸、芥酸中的一种,所述有机胺为油胺、十八胺中的一种,所述有机溶剂为三辛胺、三丁胺、1,2-十六二醇、辛胺中的一种。
其中,S2中反应温度为200-360℃,反应时间为0.5-8h。
本发明提供的含金属原子簇的磁性氧化铁纳米颗粒的制备方法,是在金属前驱体高温热解方法的基础上,通过溶剂的还原作用或掺杂,形成嵌入在氧化铁晶体中的金属原子簇,从而得到含有金属原子簇的磁性氧化铁纳米颗粒,具有简单可控的特点。
本发明提供含金属原子簇的磁性氧化铁纳米颗粒的应用,可以应用于磁共振成像、细胞长期跟踪以及磁纳米颗粒成像领域。
与现有技术相比,本发明具有以下效果:
1、本发明的含金属原子簇的磁性氧化铁纳米颗粒是一种将金属原子簇嵌入到氧化铁晶体中的磁性纳米颗粒,由于金属原子簇的嵌合使得磁性氧化铁颗粒的磁学性质得到明显的提高,而氧化铁基质又充分保证了纳米颗粒性质的稳定性,因而能够更好的应用于生物医学检测与治疗等领域;2、本发明利用金属前驱热解的方法,通过控制反应物浓度、反应时间和反应温度,可以对纳米颗粒尺寸以及形貌进行控制。3、本发明的含金属原子簇的磁性氧化铁纳米颗粒可以应用于磁共振成像、细胞长期跟踪以及磁纳米颗粒成像等领域,具有重要的现实意义。
附图说明
图1为本发明实施例1的含单质铁原子簇的磁性氧化铁纳米颗粒的透射电镜(TEM)图;
图2为本发明实施例1的含单质铁原子簇的磁性氧化铁纳米颗粒的高分辨透射电镜 (HRTEM)图;
图3为本发明实施例1的含单质铁原子簇的磁性氧化铁纳米颗粒的选区电子衍射(SAED)图;
图4为本发明实施例1的含单质铁原子簇的磁性氧化铁纳米颗粒的X射线衍射(XRD) 图;
图5为本发明实施例1的含单质铁原子簇的磁性氧化铁纳米颗粒的磁滞回线。
具体实施方式
本发明涉及含金属原子簇的磁性氧化铁纳米颗粒及其制备方法和应用,首先将氧化铁的金属前驱体、有机酸、有机胺按照比例溶于有机溶剂中形成均匀的反应体系;然后将所述反应体系在惰性气体氛围内加热到150-350℃后,加入金属原子簇前驱体,升温回流反应至前驱体全部分解,即得到含金属原子簇的磁性纳米颗粒;最后将得到的含金属原子簇的磁性纳米颗粒应用于磁共振成像、细胞长期跟踪以及磁纳米颗粒成像等领域。
在本发明中,所述金属前驱体为含铁有机配合物,包括:芥酸铁、乙酰丙酮铁Fe(acac)3、油酸铁Fe(OA)3、五羰基合铁Fe(CO)5、亚硝基羟基苯胺合铁FeCup3,但是并不局限于此。
所述金属原子簇前驱体为金属有机配合物,包括铁有机配合物,具体包括乙酰丙酮铁 Fe(acac)3、油酸铁Fe(OA)3、五羰基合铁Fe(CO)5、亚硝基羟基苯胺合铁FeCup3;钴有机配合物,具体包括Co2(CO)8、Co(acac)2;镍有机配合物,具体包括:Ni(OOCCH3)2、Ni(acac)2、钆有机配合物:Gd(OA)3、Gd(acac)3。所述金属原子簇前驱体并不局限于此。
所述有机酸为碳链长度介于6-25之间的有机酸,具体为油酸、硬脂酸、芥酸中的一种;所述有机胺为碳链长度介于6-25之间的有机胺具体为油胺、十八胺中的一种,所述有机溶剂为还原性溶剂,具体为三辛胺、三丁胺、1,2-十六二醇、辛胺中的一种。
所述氧化铁的成分为(Fe2O3)r(Fe3O4)1-r,其中r为0~1。
接下来通过具体实施例对本发明进行详细说明。
实施例1
含铁原子簇的磁性氧化铁纳米颗粒(Iron cluster iron oxide,ICIO)的制备方法:将乙酰丙酮铁Fe(acac)3(0.4mmol),油酸(6mmol),油胺(6mmol),三辛胺(30mL),在氮气氛围下搅拌充分得到均匀的混合物。将混合物加热到200℃保持1h,然后加大氮气流量加入乙酰丙酮铁Fe(acac)3(0.05mmol)再加热到340℃回流2h得到黑棕色混合物,将黑棕色混合物自然冷却到室温。取10mL酒精加到黑棕色混合物中,黑色物质被沉淀,然后进行离心分离,将离心分离得到的黑色物质溶解于10mL正己烷中,并以5000rpm转速离心处理10min除去未分散的剩余物;离心得到的产物用酒精沉淀,并以5000rpm转速离心处理10min除去溶剂,得到含铁原子簇的磁性氧化铁纳米颗粒。
对制备的含铁原子簇的磁性氧化铁纳米颗粒进行一系列表征,具体是将含铁原子簇的磁性氧化铁纳米颗粒分散在正己烷中,取2μL分散有纳米颗粒的正己烷溶液滴在镀有碳膜的Cu网上,自然干燥后做表征。图1为透射电镜图,从图1中可以看出,单质铁原子簇的磁性氧化铁纳米颗粒大小形貌均一,具有单分散性,尺寸在20nm左右;图2是高分辨透射电镜图,从图2中可以看到晶格fringes,表明此纳米颗粒结晶度很高,晶格间距为0.258 nm,符合(311)面晶面垂直间距,表明该纳米颗粒为氧化铁纳米颗粒,更重要的是,发现有Fe原子簇镶嵌在氧化铁纳米颗粒晶格中;图3为选区电子衍射,从图3中进一步证实氧化铁颗粒中有Fe原子簇;图4为XRD图,表明此纳米颗粒结晶很好,有Fe相的峰和反结晶Fe3O4相的峰;图5为VSM表征结果,说明本实施例制备的ICIO由于有单质铁原子簇嵌入氧化铁晶体内,因此稳定性好,样品放置至少1年后,测定其饱和磁化值仍高达120 emu/g,而相同条件下制备的不含铁原子簇的氧化铁颗粒,其饱和磁化值只有60emu/g,进一步说明本发明方法制备的含有单质铁原子簇的磁性氧化铁纳米颗粒具有极其高的饱和磁化值,且性质稳定,可以长期保存。
实施例2
含铁原子簇的磁性氧化铁纳米颗粒(Iron cluster iron oxide,ICIO)的制备方法:将油酸铁Fe(OA)3(0.4mmol),芥酸(8mmol),十八胺(4mmol),辛胺(40mL),在氮气氛围下搅拌充分得到均匀的混合物。将混合物加热到150℃加入保持1h,然后加大氮气流量加入乙酰丙酮铁Fe(acac)3(0.05mmol)再加热到200℃回流8h得到黑棕色混合物,将黑棕色混合物自然冷却到室温。后续处理过程与实施例1相同。
实施例3
含铁原子簇的磁性氧化铁纳米颗粒(Iron cluster iron oxide,ICIO)的制备方法:五羰基合铁Fe(CO)5(0.04mmol),硬脂酸(1mmol),油胺(10mmol),三丁胺(40mL),在氮气氛围下搅拌充分得到均匀的混合物。将混合物加热到300℃加入保持1h,然后加大氮气流量加入油酸铁Fe(OA)3(0.005mmol)再加热到360℃回流0.5h得到黑棕色混合物,将黑棕色混合物自然冷却到室温。后续处理过程与实施例1相同。
实施例4
含钴原子簇的磁性氧化铁纳米颗粒(Cobalt cluster iron oxide,CCIO)的制备方法:将乙酰丙酮铁Fe(acac)3(8mmol),油酸(6mmol),油胺(6mmol),三辛胺(30mL),在氮气氛围下搅拌充分得到均匀的混合物。将混合物加热到200℃保持1h,然后加大氮气流量加入羰基钴Co2(CO)8(1mmol)再加热到340℃回流2h得到黑棕色混合物,将黑棕色混合物自然冷却到室温后进行后续处理。后续处理过程与实施例1相同,后续处理后即得到含钴原子簇的磁性氧化铁纳米颗粒。
实施例5
含镍原子簇的磁性氧化铁纳米颗粒(Nickel cluster iron oxide,NCIO)的制备方法:将乙酰丙酮铁Fe(acac)3(8mmol),油酸(6mmol),油胺(6mmol),三辛胺(30mL),在氮气氛围下搅拌充分得到均匀的混合物。将混合物加热到200℃保持1h,然后加大氮气流量加入乙酰丙酮镍Ni(acac)2(1mmol),再加热到340℃回流2h得到黑棕色混合物,将黑棕色混合物自然冷却到室温后进行后续处理。后续处理过程与实施例1相同,后续处理后即得到含镍原子簇的磁性氧化铁纳米颗粒。
实施例6
含铁镍原子簇的磁性氧化铁纳米颗粒的制备方法:将乙酰丙酮铁Fe(acac)3(8mmol),油酸(6mmol),油胺(6mmol),三辛胺(30mL),在氮气氛围下搅拌充分得到均匀的混合物。将混合物加热到200℃保持1h,然后加大氮气流量加入乙酰丙酮镍Ni(acac)2(0.5mmol)、乙酰丙酮铁Fe(acac)3(0.5mmol)再加热到340℃回流2h得到黑棕色混合物,将黑棕色混合物自然冷却到室温后进行后续处理。后续处理过程与实施例1相同,后续处理后即得到含钴原子簇的磁性氧化铁纳米颗粒。
实施例7
取1mL实施例1制备的含铁原子簇磁性氧化铁纳米颗粒(ICIO,20nm)的水溶液,其中铁含量为0.1mg/mL;另取1mL不含铁原子簇磁性氧化铁纳米颗粒(SPIO,20nm) 的水溶液,其中铁含量同样为0.1mg/mL,分别加入到15mL试管中,并将试管放置于磁热仪的磁线圈里,从而在试管外部加上中频交变磁场(频率为488kHz,场强为600Oe),利用光纤热电偶探头来测量温度变化,测定磁性纳米颗粒的比吸收速率(SAR),SAR的定义是在单位时间内,单位质量的铁在交变磁场中所能产生的热量,单位是瓦特/克(Watt/g),计算如公式(1)所示,该计算值可以评价磁性纳米颗粒的磁热转换效率。本实施例中所用的磁热仪器由深圳市双平电源技术有限公司生产,型号为SPG-10AB-II,该仪器同时还与光纤探头连接,以测试样品溶液的温度。
比吸收速率(SAR)的计算:
其中:C为水溶液的比热容(Cwater=4.18J/(g·℃)),ΔT/Δt为升温曲线中的初始斜率。mFe为磁性纳米颗粒溶液中铁原子的浓度。本实施例中磁热仪器的测试结果发现含有铁原子簇磁性氧化铁纳米颗粒(ICIO)和不含铁原子簇磁性氧化铁纳米颗粒(SPIO)水溶液在加磁场30秒后,水溶液的温度分别由27.6℃上升至44.2℃和27.8℃,计算得到SAR 值分别为:25600W/g和228W/g,充分说明含有铁原子簇磁性氧化铁纳米颗粒磁热转换效率远远高于相同浓度的不含有铁原子簇磁性氧化铁纳米颗粒。
实施例8
将实施例1制备的含有铁原子簇磁性氧化铁纳米颗粒(ICIO)和不含铁原子簇磁性氧化铁纳米颗粒(SPION)分散在琼脂糖凝胶中,使其Fe浓度分别为0.01,0.025,0.05,0.1,0.25, 0.5mM。分别取15mL装入20mL玻璃瓶中,以琼脂糖凝胶为对照样品,使用7T小动物磁共振成像仪(BioSpec 70/20USR,Bruker,Germany)进行扫描。MRI扫描参数为:TR=2900ms,TE=40.06ms,field of view=35mm×35mm,matrix size=256×256,flip angle=90° and NEX=3。得到样品磁共振扫描图像后,采用Matlab软件,使用Levenberg-Margardt法计算出不同浓度梯度样品的弛豫时间T2值,进而求出弛豫速率r2=1/T2。经计算含有铁原子簇磁性氧化铁纳米颗粒(ICIO)和不含铁原子簇磁性氧化铁纳米颗粒(SPION)的r2分别为1060 mM-1S-1和185mM-1S-1,说明含有铁原子簇磁性氧化铁纳米颗粒(ICIO)的r2是不含铁原子簇磁性氧化铁纳米颗粒(SPION)的r2的5倍以上,说明含铁原子簇磁性氧化铁纳米颗粒MRI的成像性能远远高于不含铁原子簇磁性氧化铁纳米颗粒。
实施例9
将实施例1制备的含有铁原子簇磁性氧化铁纳米颗粒用于磁纳米颗粒成像,利用MPI 扫描仪(Magnetic Insight Inc,MOMENTUMTM Imager),频率是45KHz、磁梯度强度(magnetic gradient strenght)为5.7T/m,数据用VivoQuant软件处理。在0.5mg/ml浓度下测得样品信号强度可以达到1169,而不含铁原子簇磁性氧化铁纳米颗粒信号强度只有192,含有铁原子簇磁性氧化铁纳米颗粒信号强度是普通磁性氧化铁纳米颗粒造影剂的6倍,成像性能优越。
应当指出,对于本领域的普通技术人员来说,在不脱离本发明创造构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。
Claims (8)
1.含金属原子簇的磁性氧化铁纳米颗粒,其特征在于,所述金属原子簇嵌合在氧化铁晶体基质中,且所述金属原子簇在含金属原子簇的磁性氧化铁纳米颗粒中的含量占比为0.1-15%,所述金属原子簇嵌合在氧化铁晶体基质中是指金属原子簇是镶嵌在氧化铁的晶格中;
所述金属原子簇是由金属原子M形成的Mx原子簇,x的范围为3-100,所述M为稀土金属、Fe、Co、Ni中的一种或两种;
所述金属原子簇的粒径大小为0.2-5 nm,所述氧化铁晶体基质的粒径范围为2-100nm。
2.根据权利要求1所述的含金属原子簇的磁性氧化铁纳米颗粒,其特征在于,所述稀土金属为Nd、Sm、Tb、Dy、Ho、Er、Tm、Yb、Ce中的一种或两种。
3.权利要求1或2所述的含金属原子簇的磁性氧化铁纳米颗粒的制备方法,其特征在于,包括以下步骤:
S1、将氧化铁的金属前驱体、有机酸、有机胺按照比例溶于有机溶剂中形成均匀的反应体系;
S2、将S1中所述反应体系在惰性气体氛围内加热到150-350℃后,加入金属原子簇前驱体,升温回流反应至金属原子簇前驱体全部分解,即得到含金属原子簇的磁性纳米颗粒。
4.根据权利要求3所述的含金属原子簇的磁性氧化铁纳米颗粒的制备方法,其特征在于,所述金属前驱体为含铁有机配合物,所述金属原子簇前驱体为金属有机配合物;
其中,所述含铁有机配合物为:芥酸铁、乙酰丙酮铁Fe(acac)3、油酸铁Fe(OA)3、五羰基合铁Fe(CO)5或亚硝基羟基苯胺合铁FeCup3;
其中,所述金属有机配合物为:乙酰丙酮铁Fe(acac)3、油酸铁Fe(OA)3、五羰基合铁Fe(CO)5、亚硝基羟基苯胺合铁FeCup3、Co2(CO)8、Co(acac)2、Ni(OOCCH3)2、Ni(acac)2、油酸稀土配合物、乙酰丙酮稀土配合物中的一种或两种。
5.根据权利要求3所述的含金属原子簇的磁性氧化铁纳米颗粒的制备方法,其特征在于,所述有机酸与有机胺的摩尔比为1:0.5-10;所述有机酸与有机溶剂的体积比为1:1-100;所述有机胺与有机溶剂的体积比为1:1-100;所述金属前驱体的浓度为0.01-1 mol/L。
6.根据权利要求5所述的含金属原子簇的磁性氧化铁纳米颗粒的制备方法,其特征在于,所述有机酸为碳链长度介于6-25之间的有机酸,所述有机胺为碳链长度介于6-25之间的有机胺,所述有机溶剂为还原性溶剂。
7.根据权利要求3所述的含金属原子簇的磁性氧化铁纳米颗粒的制备方法,其特征在于,S2中反应温度为200-360 ℃,反应时间为0.5-8h。
8.含金属原子簇的磁性氧化铁纳米颗粒的应用,其特征在于,将权利要求1或2所述的含金属原子簇的磁性氧化铁纳米颗粒用于共振成像、细胞长期跟踪以及磁纳米颗粒成像领域。
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