WO2015090145A1 - 一种负载贵金属量子点的磁性复合微球及其制备方法 - Google Patents

一种负载贵金属量子点的磁性复合微球及其制备方法 Download PDF

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WO2015090145A1
WO2015090145A1 PCT/CN2014/093039 CN2014093039W WO2015090145A1 WO 2015090145 A1 WO2015090145 A1 WO 2015090145A1 CN 2014093039 W CN2014093039 W CN 2014093039W WO 2015090145 A1 WO2015090145 A1 WO 2015090145A1
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magnetic
noble metal
loaded
metal quantum
quantum dots
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戴李宗
陈凌南
吴悦广
曾碧榕
叶华立
陈国荣
许一婷
罗伟昂
项佳懿
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Xiamen University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/42—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of organic or organo-metallic materials, e.g. graphene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene

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  • the invention belongs to the technical field of composite materials, and particularly relates to a magnetic composite microsphere loaded with precious metal quantum dots and a preparation method thereof.
  • Quantum dots are nanocrystals with a radius smaller or closer to the Bohr radius. They are a new class of materials that differ from the bulk and are different from the molecular and atomic properties. They have unique quantum size effects and surface enhancement effects. Compared with traditional organic dyes, the absorption spectrum of quantum dots depends on their particle size and the distance between quantum dots, covering from the ultraviolet to the infrared region, excellent spectral characteristics, stable photochemical properties, in immunoassays, cell and in vivo imaging, Good applications in areas such as gene analysis and tumor hyperthermia.
  • Magnetic microspheres are a kind of functional materials with great application prospects. Besides the characteristics of general nanomaterials, they also exhibit new and different characteristics from traditional magnetic materials, such as superparamagnetism, low Curie temperature and high magnetic susceptibility. Wait. By adsorbing the target molecule or target cell on the magnetic microsphere through a functional group, protein purification, nucleic acid separation, and drug targeted release can be achieved under the action of an external magnetic field.
  • a magnetic silica pellet was prepared by the stober method, followed by utilization.
  • the layer-by-layer self-assembly technique adsorbs a layer of polyelectrolyte and CdTe quantum dots on the outside of the silica beads, and finally coats a layer of silicon dioxide to obtain a luminescent composite microsphere.
  • the magnetic content of the microsphere is low and unregulated, and has certain limitations.
  • the composite microspheres are based on amino-functionalized silica beads, and the surface is loaded with brominated isobutyric acid-stabilized Fe 3 O 4 nanoparticles and nano precious metals, which can effectively kill cancer by controlling external light intensity. cell.
  • the disadvantage is that the preparation process is complicated, and the silica substrate can not be stably existed in an alkaline environment, and the application is limited.
  • He Rong et al. (Preparation method of fluorescent magnetic multifunctional nanomaterial, Chinese patent, publication number CN 1831079 A)
  • the surface of Fe 3 O 4 is modified by an aminosilane coupling agent, and the quantum dots are passed through the electrostatic interaction between the amino group and the carboxyl group. Directly assembled on the surface of Fe 3 O 4 particles. In this way, the amount of adsorption of quantum dots is difficult to control, and the two particles are sharply degraded due to direct contact.
  • Another object of the present invention is to provide a method for preparing the above-described magnetic composite microspheres loaded with noble metal quantum dots.
  • a magnetic composite microsphere loaded with noble metal quantum dots comprising magnetic polymer microspheres and noble metal quantum dots supported on the surface of the magnetic polymer microspheres.
  • the magnetic polymer microspheres comprise a core and a shell
  • the core is a polystyrene sphere enclosing magnetic ferroferric oxide
  • the shell is polymaleic acid Alcohol diester.
  • the noble metal is one of gold, silver, platinum and palladium.
  • a method for preparing the above magnetic composite microspheres loaded with noble metal quantum dots comprising the following steps:
  • the step (1) is to dissolve the maleic acid iso-diester diester in deionized water, stir for 1 to 2 hours, then add Fe 3 O 4 , styrene monomer and continue to stir 6 After ⁇ 12 hours, the initiator was heated to 60-65 ° C for 12-24 hours to obtain a magnetic polymer microsphere emulsion.
  • the content of the maleic acid isoester, Fe 3 O 4 and styrene monomer is 0.1% to 1 wt%, 0.5% to 5 wt% and 2% to 10 wt%, respectively, and the balance is deionized.
  • Water; the initiator is a water-soluble initiator, the amount of which is 0.1% to 1% by weight of the styrene monomer; the Fe 3 O 4 is prepared by chemical coprecipitation, and is modified by oleic acid, oleic acid and The mass ratio of Fe 3 O 4 is 1:1.05 to 1:1.15.
  • the step (2) is taking the magnetic polymer microsphere emulsion, adding a noble metal acid aqueous solution and stirring 1 ⁇ 3 After an hour, the sodium borohydride aqueous solution was added and stirring was continued for 2 to 6 hours to obtain magnetic polymer microspheres loaded with noble metal quantum dots.
  • the noble metal acid compound is one of chloroauric acid, silver nitrate, chloroplatinic acid, and chloropalladium acid, and the amount thereof is 0.1% to 1% by weight of the magnetic polymer microsphere emulsion; the sodium borohydride is added. The amount is from 0.5% to 5% by weight of the magnetic polymer microsphere emulsion.
  • the step (3) is to centrifugally separate the magnetic polymer microsphere emulsion loaded with the noble metal quantum dots in the step (2) to remove the precious metal quantum dots free in the water, and then redisperse them.
  • the ionic water add the same kind of noble metal acid aqueous solution and stir for 0.5 ⁇ 2 hours, then add the ascorbic acid aqueous solution and stir for 2 ⁇ 4 hours to realize the growth of the precious metal quantum dots supported on the surface of the magnetic polymer microspheres, and the size and shape of the quantum dots change. .
  • the same noble metal acid compound is added in an amount of 0.5% to 3% by weight of the polymer microsphere emulsion; and the ascorbic acid is added in an amount of 0.5% to 3% by weight of the polymer microsphere emulsion.
  • the magnetic composite microsphere of the present invention uses magnetic polymer microspheres as a carrier to carry precious metal quantum dots on the surface, has excellent magnetic properties, can control its moving direction by the action of an external magnetic field, and absorbs in the infrared region.
  • the ball can effectively realize the conversion between light and heat, and has broad application prospects in the fields of tumor hyperthermia;
  • the preparation method of the present invention comprises a microemulsion method for synthesizing magnetic polymer microspheres in one step, comprising Fe 3 O 4 , a polystyrene core layer and a maleate shell layer.
  • the composite microspheres which are absorbed in different light wave regions are obtained by directly reducing the noble metal salt loading quantum dots on the surface of the magnetic polymer microspheres and regulating the growth of the quantum dots. Its dual optical and magnetic properties are expected to find important applications in biomedical and other fields.
  • Figure 1 is a TEM image of a magnetic polymer microsphere in Example 1 of the present invention.
  • Example 2 is a TEM image of a magnetic composite microsphere loaded with a noble metal quantum dot prepared in the step (2) of Example 1 of the present invention
  • Example 3 is a TEM image of a magnetic composite microsphere loaded with a noble metal quantum dot prepared in the step (3) of Example 1 of the present invention
  • Example 4 is a hysteresis loop diagram of a magnetic composite microsphere loaded with a noble metal quantum dot prepared in Example 1 of the present invention.
  • Figure 5 is an embodiment 2 ⁇ 4 of the present invention
  • the UV-vis absorption spectrum of the prepared magnetic composite microspheres loaded with noble metal quantum dots, and the reference group are magnetic polymer microspheres loaded with noble metal quantum dots.
  • step (1) Take 1 mL of the magnetic polymer microsphere emulsion in step (1) and dilute it to 10 mL with deionized water; add 1 mL to the concentration 10 times with stirring. Methyl/L aqueous solution of chloroauric acid; after 2 hours, add 1 mL to a concentration of 20 A millimolar/L aqueous solution of sodium borohydride was stirred at room temperature for 6 hours to obtain magnetic polymer microspheres loaded with noble metal quantum dots. The obtained microspheres were characterized by transmission electron microscopy (TEM). As shown in Fig.
  • TEM transmission electron microscopy
  • the magnetic polymer microsphere emulsion loaded with noble metal quantum dots in step (2) is centrifugally separated to remove precious metal quantum dots free in water, and then redispersed in 10 In mL of deionized water; add 2.0 mL of 10 mmol/L aqueous chloroauric acid solution, stir for 1 hour, then add 2.5 mL to a concentration of 10
  • the mmol/L aqueous solution of ascorbic acid was stirred for 3 hours to achieve growth of precious metal quantum dots supported on the surface of the magnetic polymer microspheres, and the size and shape of the quantum dots were changed.
  • the obtained microspheres were characterized by transmission electron microscopy (TEM). As shown in Fig. 3, the size and shape of the precious metal quantum dots undergoing regrowth process changed significantly.
  • the UV-visible absorption spectrum of the composite microspheres is from Unico. UV-vis 2802PCS is characterized. With the growth of noble metal quantum dots, the absorption wavelength is significantly red-shifted to about 800 nm.
  • the amount of the aqueous chloroauric acid solution in the step (3) is changed to 0.5 mL, 1.0 mL, and 1.5, respectively.
  • the absorption wavelengths of mL, UV-vis are 530 nm, 560 nm, and 690 nm, as shown in Figure 5.
  • the noble metal acid species in the step (2) are changed to silver nitrate, chloroplatinic acid and chloropalladium acid to obtain different types of composite microspheres.
  • the results are shown in the following table: Example Noble metal acid solution aqueous solution / 2mL Ascorbic acid aqueous solution / mL UV-vis absorption wavelength / nm 5 Silver nitrate 2 730 6 Chloroplatinic acid 2 780 7 Chloro palladium acid 2 760
  • the magnetic composite microsphere of the invention adopts magnetic polymer microspheres as a carrier, and carries precious metal quantum dots on the surface, has excellent magnetic properties, can control the moving direction by the action of an external magnetic field; the microspheres absorbed in the infrared region can be Effectively achieve the conversion between light and heat.
  • the composite microspheres which are absorbed in different light wave regions are obtained by directly reducing the noble metal salt loading quantum dots on the surface of the magnetic polymer microspheres and regulating the growth of the quantum dots.

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Abstract

本发明公开了一种负载贵金属量子点的磁性复合微球及其制备方法，其包括磁性聚合物微球和负载在该磁性聚合物微球表面的贵金属量子点。本发明的磁性复合微球以磁性聚合物微球为载体，在表面负载贵金属量子点，具优异的磁学性能，可以通过外部磁场的作用控制其移动方向；处在红外区域吸收的微球可以有效的实现光-热之间的转换，在肿瘤热疗等领域的应用前景广阔。

Description

一种负载贵金属量子点的磁性复合微球及其制备方法 技术领域
本发明属于复合材料技术领域，具体涉及一种负载贵金属量子点的磁性复合微球及其制备方法。
背景技术
近年来，贵金属量子点因其优异特性吸引了广大研究人员的兴趣。量子点是指半径小于或接近激光波尔半径的纳米晶，是一类不同于本体又异于分子、原子特性的新型材料，具有独特的量子尺寸效应和表面增强效应。与传统的有机染料相比，量子点的吸收光谱取决于其粒径以及量子点之间的距离，覆盖从紫外到红外区域，光谱特征优异、光化学性质稳定，在免疫检测、细胞及活体成像、基因分析和肿瘤热疗等领域具有很好的应用。
磁性微球是一类极具应用前景的功能材料，它除了一般纳米材料所具备的特性外，还呈现出不同与传统磁性材料的新特性，如超顺磁性、低居里温度和高磁化率等。通过将目标分子或目标细胞通过功能基团吸附在磁性微球上，在外部磁场作用下可以实现蛋白质提纯、核酸分离和药物靶向释放等。
将量子点和磁性微球结合在一起，得到一种既具有量子点光学效应，又兼具磁性能的复合微球，具有诱人的应用前景。在这一领域，Wang等（D. Wang, J. He, N. Rosenzweig et al, Nano. Lett., 2004, 4, 409-412. ）将CdSe/ZnS 量子点直接通过巯基吸附在聚合物包裹的γ-Fe2O3表面，并将其用于癌细胞的荧光检测和磁分离。Salgueirino等（V. Salgueirino-Maceira, M. A. Correa-Duarte, et al, Adv. Funct. Mater., 2006, 16, 509-514.）首先采用stober法制备了一种磁性二氧化硅小球，其次利用层层自组装技术在二氧化硅小球的外面吸附一层聚电解质和CdTe量子点，最后再包裹上一层二氧化硅得到一种发冷光的复合微球。这种方法微球的磁含量较低且无法调控，具有一定的局限性。Kim等（J.Kim, S. Park, et al, Angew. Chem. Int. Ed., 2006, 45, 7754-7758.）报道了一种兼具磁共振成像和热成像功能的复合微球。这种复合微球以氨基功能化的二氧化硅小球为基体，表面负载了溴代异丁酸稳定的Fe3O4纳米粒子和纳米贵金属，通过外部光强的控制可以有效的杀死癌细胞。其缺点是制备工艺复杂，且以二氧化硅为基体无法在碱性环境中稳定存在，应用受到一定的限制。贺蓉等（荧光磁性多功能纳米材料的制备方法，中国专利，公开号CN 1831079 A）利用氨硅烷偶联剂修饰Fe3O4表面，再通过氨基和羧基之间的静电作用，将量子点直接组装在Fe3O4粒子表面。这种方法量子点的吸附量难以控制，且两种粒子由于直接接触导致荧光强度急剧下降。
目前，以磁含量可控的具有核-壳结构的磁性聚合物为载体，兼具可调光学和磁学性能的复合微球尚未见报道。
发明内容
本发明的目的在于克服现有技术缺陷，提供一种负载贵金属量子点的磁性复合微球。
本发明的另一目的在于提供上述负载贵金属量子点的磁性复合微球的制备方法。
本发明的技术方案如下：
一种负载贵金属量子点的磁性复合微球，包括磁性聚合物微球和负载在该磁性聚合物微球表面的贵金属量子点。
在本发明的一个优选实施方案中，所述磁性聚合物微球包括一核心和一外壳，所述核心为一内包磁性四氧化三铁的聚苯乙烯球，所述外壳为聚马来酸异醇双酯。
在本发明的一个优选实施方案中，所述贵金属为金、银、铂和钯中的一种。
本发明微球的制备方法如下：
一种上述负载贵金属量子点的磁性复合微球的制备方法，包括如下步骤：
（1）制备磁性聚合物微球；
（2）将贵金属量子点负载在上述磁性聚合物微球上；
（3）根据需要控制贵金属量子点的尺寸和形状。
在本发明的一个优选实施方案中，所述步骤（1）为将马来酸异醇双酯溶于去离子水中，搅拌1~2小时后加入Fe3O4、苯乙烯单体继续搅拌6~12小时后加入引发剂升温至60~65℃反应12~24小时即得到磁性聚合物微球乳液。
进一步优选的，所述马来酸异醇双酯、Fe3O4和苯乙烯单体的含量分别为0.1%~1wt%、0.5%~5wt%和2%~10wt%，余量为去离子水；所述引发剂为水溶性引发剂，其用量为苯乙烯单体的0.1%~1wt%；所述Fe3O4采用化学共沉淀法制备，并利用油酸加以改性，油酸与Fe3O4的质量比为1:1.05~1:1.15。
进一步优选的，所述引发剂为过硫酸钾或过硫酸铵。
在本发明的一个优选实施方案中，所述步骤（2）为取所述磁性聚合物微球乳液，加入贵金属酸化物水溶液搅拌1~3 小时后加入硼氢化钠水溶液继续搅拌2~6小时即得到负载贵金属量子点的磁性聚合物微球。
进一步优选的，所述贵金属酸化物为氯金酸、硝酸银、氯铂酸、氯钯酸中的一种，加入量占磁性聚合物微球乳液的0.1%~1wt%；硼氢化钠的加入量占磁性聚合物微球乳液的0.5%~5wt%。
在本发明的一个优选实施方案中，所述步骤（3）为将步骤（2）中负载贵金属量子点的磁性聚合物微球乳液离心分离除去游离在水中的贵金属量子点，然后重新分散在去离子水中，加入同种贵金属酸化物水溶液搅拌0.5~2小时后加入抗坏血酸水溶液继续搅拌2~4小时即可实现负载在磁性聚合物微球表面贵金属量子点的生长、量子点的尺寸和形状发生改变。
进一步优选的，所述同种贵金属酸化物的加入量占聚合物微球乳液的0.5%~3wt%；抗坏血酸的加入量占聚合物微球乳液的0.5%~3wt%。
本发明的有益效果是：
1、本发明的磁性复合微球以磁性聚合物微球为载体，在表面负载贵金属量子点，具优异的磁学性能，可以通过外部磁场的作用控制其移动方向；处在红外区域吸收的微球可以有效的实现光—热之间的转换，在肿瘤热疗等领域的应用前景广阔；
2、本发明的其制备方法采用微乳液法一步合成磁性聚合物微球，包含Fe3O4、聚苯乙烯核层和马来酸酯壳层三部分。通过在磁性聚合物微球表面直接还原贵金属盐负载量子点并调控量子点的生长得到在不同光波区域均有吸收的复合微球。其光学和磁学双重性能有望在生物医疗等领域得到重要的应用。
附图说明
图1为本发明的实施例1中磁性聚合物微球的TEM图。
图2为本发明的实施例1中步骤（2）制备的负载贵金属量子点的磁性复合微球的TEM图；
图3为本发明的实施例1中步骤（3）制备的负载贵金属量子点的磁性复合微球的TEM图；
图4为本发明的实施例1制备的负载贵金属量子点的磁性复合微球的磁滞回线图。
图5为本发明的实施例 2~4 制备的负载贵金属量子点的磁性复合微球的UV-vis吸收光谱，参照组为负载贵金属量子点的磁性聚合物微球。
具体实施方式
以下通过具体实施方式结合附图对本发明的技术方案进行进一步的说明和描述。
实施例1
（1）磁性聚合物微球的制备
40 mg马来酸异醇双酯溶于40 mL去离子水中，机械搅拌2小时，加入0.5 g Fe3O4、3 g 苯乙烯单体，通氮气，继续搅拌12小时后加入30 mg过硫酸钾升温至65 ℃反应24小时得到具有核壳结构的磁性聚合物微球乳液。通过透射电镜（TEM）对所得微球进行结构表征，如图1，磁性聚合物微球的整体尺寸为250nm左右，其中核层尺寸为150 nm左右，壳层厚度为50 nm左右；Fe3O4 包含在微球内部，尺寸为8 nm左右。
（2）贵金属量子点的负载
取1 mL步骤（1）中磁性聚合物微球乳液用去离子水稀释至10 mL；搅拌下逐滴滴加1 mL浓度为10 mmol/L的氯金酸水溶液；2小时后加入1 mL浓度为20 mmol/L的硼氢化钠水溶液，常温搅拌6小时后即得到负载贵金属量子点的磁性聚合物微球。通过透射电镜（TEM）对所得微球进行结构表征，如图2所示，贵金属量子点均匀负载在磁性聚合物微球表面；磁性能由SQUID超导量子干涉磁强计进行表征，剩余磁化强度和矫顽力均接近于0，几乎无磁滞存在，具有超顺磁性。
（3）贵金属量子点的生长
将步骤（2）中负载贵金属量子点的磁性聚合物微球乳液离心分离除去游离在水中的贵金属量子点，然后重新分散在10 mL去离子水中；加入2.0 mL浓度为10 mmol/L的氯金酸水溶液，搅拌1小时后加入2.5 mL浓度为10 mmol/L的抗坏血酸水溶液继续搅拌3小时即可实现负载在磁性聚合物微球表面贵金属量子点的生长，量子点的尺寸和形状发生改变。通过透射电镜（TEM）对所得微球进行结构表征，如图3所示，经过再生长过程的贵金属量子点尺寸和形状发生明显的变化。如图4所示，复合微球的紫外-可见吸收光谱由Unico UV-vis 2802PCS进行表征，随着贵金属量子点的生长，吸收波长发生明显的红移至800 左右nm。
实施例2~4
同实施例1工艺，改变步骤（3）中氯金酸水溶液的加入量依次为0.5 mL、1.0 mL、1.5 mL，UV-vis的吸收波长依次为530 nm、560 nm、690 nm，如图5所示。
实施例5~7
同实施例1工艺，改变步骤（2）中贵金属酸化物种类分别为硝酸银、氯铂酸、氯钯酸，得到不同类型的复合微球，结果如下表所示：
实施例 贵金属酸化物水溶液/2mL 抗坏血酸水溶液/mL UV-vis 吸收波长/ nm
5 硝酸银 2 730
6 氯铂酸 2 780
7 氯钯酸 2 760
以上所述，仅为本发明的较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。
工业实用性
本发明的磁性复合微球以磁性聚合物微球为载体，在表面负载贵金属量子点，具优异的磁学性能，可以通过外部磁场的作用控制其移动方向；处在红外区域吸收的微球可以有效的实现光—热之间的转换。通过在磁性聚合物微球表面直接还原贵金属盐负载量子点并调控量子点的生长得到在不同光波区域均有吸收的复合微球。

Claims (10)

  1. 一种负载贵金属量子点的磁性复合微球，其特征在于：包括磁性聚合物微球和负载在该磁性聚合物微球表面的贵金属量子点，所述磁性聚合物微球包括一核心和一外壳，所述核心为一内包磁性四氧化三铁的聚苯乙烯球，所述外壳为聚马来酸异醇双酯。
  2. 如权利要求1所述的一种负载贵金属量子点的磁性复合微球，其特征在于：所述贵金属为金、银、铂和钯中的一种。
  3. 一种如权利要求1或2所述的负载贵金属量子点的磁性复合微球的制备方法，其特征在于：包括如下步骤：
    （1）制备磁性聚合物微球；
    （2）将贵金属量子点负载在上述磁性聚合物微球上；
    （3）根据需要控制贵金属量子点的尺寸和形状。
  4. 如权利要求3所述的一种负载贵金属量子点的磁性复合微球的制备方法，其特征在于：所述步骤（1）为将马来酸异醇双酯溶于去离子水中，搅拌1~2小时后加入Fe3O4、苯乙烯单体继续搅拌6~12小时后加入引发剂升温至60~65℃反应12~24小时即得到磁性聚合物微球乳液。
  5. 如权利要求4所述的一种负载贵金属量子点的磁性复合微球的制备方法，其特征在于：所述马来酸异醇双酯、Fe3O4和苯乙烯单体的含量分别为0.1%~1wt%、0.5%~5wt%和2%~10wt%，余量为去离子水；所述引发剂为水溶性引发剂，其用量为苯乙烯单体的0.1%~1wt%；所述Fe3O4采用化学共沉淀法制备，并利用油酸加以改性，油酸与Fe3O4的质量比为1:1.05~1:1.15。
  6. 如权利要求5所述的一种负载贵金属量子点的磁性复合微球的制备方法，其特征在于：所述引发剂为过硫酸钾或过硫酸铵。
  7. 如权利要求4所述的一种负载贵金属量子点的磁性复合微球的制备方法，其特征在于：所述步骤（2）为取所述磁性聚合物微球乳液，加入贵金属酸化物水溶液搅拌1~3 小时后加入硼氢化钠水溶液继续搅拌2~6小时即得到负载贵金属量子点的磁性聚合物微球。
  8. 如权利要求7所述的一种负载贵金属量子点的磁性复合微球的制备方法，其特征在于：所述贵金属酸化物为氯金酸、硝酸银、氯铂酸、氯钯酸中的一种，加入量占磁性聚合物微球乳液的0.1%~1wt%；硼氢化钠的加入量占磁性聚合物微球乳液的0.5%~5wt%。
  9. 如权利要求7所述的一种负载贵金属量子点的磁性复合微球的制备方法，其特征在于：所述步骤（3）为将步骤（2）中负载贵金属量子点的磁性聚合物微球乳液离心分离除去游离在水中的贵金属量子点，然后重新分散在去离子水中，加入同种贵金属酸化物水溶液搅拌0.5~2小时后加入抗坏血酸水溶液继续搅拌2~4小时即可实现负载在磁性聚合物微球表面贵金属量子点的生长、量子点的尺寸和形状发生改变。
  10. 如权利要求9所述的一种负载贵金属量子点的磁性复合微球的制备方法，其特征在于：所述同种贵金属酸化物的加入量占聚合物微球乳液的0.5%~3wt%；抗坏血酸的加入量占聚合物微球乳液的0.5%~3wt%。
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