CN114790391A - Hydrophilic modification method of oleic acid-capped up-conversion nanoparticles based on ligand oxidation - Google Patents
Hydrophilic modification method of oleic acid-capped up-conversion nanoparticles based on ligand oxidation Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 54
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 title claims abstract description 37
- 230000003647 oxidation Effects 0.000 title claims abstract description 32
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 28
- 239000003446 ligand Substances 0.000 title claims abstract description 26
- 238000002715 modification method Methods 0.000 title claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 22
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims abstract description 22
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 21
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 21
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000005642 Oleic acid Substances 0.000 claims abstract description 21
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 9
- -1 manganate ions Chemical class 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 claims 2
- 238000000926 separation method Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229910003317 GdCl3 Inorganic materials 0.000 description 3
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 description 3
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 description 3
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000001215 fluorescent labelling Methods 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- NALMPLUMOWIVJC-UHFFFAOYSA-N n,n,4-trimethylbenzeneamine oxide Chemical compound CC1=CC=C([N+](C)(C)[O-])C=C1 NALMPLUMOWIVJC-UHFFFAOYSA-N 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 235000015281 sodium iodate Nutrition 0.000 description 1
- 239000011697 sodium iodate Substances 0.000 description 1
- 229940032753 sodium iodate Drugs 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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Abstract
Description
技术领域technical field
本发明属于新材料领域，具体涉及一种基于配体氧化的油酸封端上转换发光纳米颗粒的亲水性修饰方法。The invention belongs to the field of new materials, and in particular relates to a hydrophilic modification method of oleic acid-capped up-conversion luminescent nanoparticles based on ligand oxidation.
背景技术Background technique
上转换发光材料因其独特的发光特性，在生物成像、荧光标记、温度传感、生物探针、生物传感等领域有着广泛的应用前景，但是由于高质量的上转换发光纳米颗粒的制备多涉及高温溶剂热法制备工艺，使用这种方法制备得到的纳米颗粒被油酸封端具有疏水性，而对疏水性纳米颗粒进行亲水性修饰是生物应用的前提条件。Upconversion luminescent materials have broad application prospects in bioimaging, fluorescent labeling, temperature sensing, biological probes, biosensing and other fields due to their unique luminescent properties. It involves a high-temperature solvothermal preparation process. The nanoparticles prepared by this method are end-capped with oleic acid and have hydrophobicity, and the hydrophilic modification of hydrophobic nanoparticles is a prerequisite for biological applications.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供一种基于配体氧化的油酸封端上转换发光纳米颗粒的亲水性修饰方法，使得由高温溶剂热法合成得到的油酸封端的疏水性上转换发光纳米颗粒具备亲水性，从而进一步增加上转换发光纳米颗粒的生物应用范围。The object of the present invention is to provide a hydrophilic modification method of oleic acid-terminated upconversion luminescent nanoparticles based on ligand oxidation, so that the oleic acid-terminated hydrophobic upconversion luminescent nanoparticles synthesized by high temperature solvothermal method have hydrophilic, thereby further increasing the range of biological applications of upconversion luminescent nanoparticles.
本发明的技术方案如下：The technical scheme of the present invention is as follows:
一种基于配体氧化的油酸封端上转换发光纳米颗粒的亲水性修饰方法，所述修饰方法包括以下步骤：A method for hydrophilic modification of oleic acid end-capped up-conversion luminescent nanoparticles based on ligand oxidation, the modification method comprises the following steps:
（1）三颈烧瓶中加入氯化稀土、十八烯（ODE），油酸（OA），搅拌状态下升温至160℃，反应40min后，降至室温加入氟化钠，室温状态下搅拌20min后升温至310℃，反应30min后，降至室温，离心分离，将离心物分散在环己烷中，得到纳米颗粒的胶体溶液；(1) Add rare earth chloride, octadecene (ODE), and oleic acid (OA) to the three-necked flask, heat up to 160°C under stirring, and react for 40 minutes, then drop to room temperature, add sodium fluoride, and stir at room temperature for 20 minutes Then the temperature is raised to 310°C, and after 30 minutes of reaction, the temperature is lowered to room temperature, and centrifugation is performed, and the centrifuge is dispersed in cyclohexane to obtain a colloidal solution of nanoparticles;
（2）烧杯A中加入步骤（1）中得到的上转换发光纳米颗粒胶体溶液，搅拌状态下加入丙酮；(2) Add the upconversion luminescent nanoparticle colloidal solution obtained in step (1) into the beaker A, and add acetone under stirring;
（3）烧杯B中加入高锰酸钾和高碘酸钠，加入去离子水搅拌至固体完全溶解；(3) Add potassium permanganate and sodium periodate to beaker B, add deionized water and stir until the solid is completely dissolved;
（4）将烧杯B中的溶液滴加入烧杯A中，室温下，搅拌24h后，用去离子水洗涤两次，并将离心物分散在10mL去离子水中，得到上转换发光纳米颗粒的水溶液后，可在此基础上开展生物应用。(4) The solution in beaker B was added dropwise to beaker A, and after stirring for 24 hours at room temperature, washed twice with deionized water, and the centrifuge was dispersed in 10 mL of deionized water to obtain an aqueous solution of upconversion luminescent nanoparticles. , on which biological applications can be developed.
进一步地，所述步骤（1）中，氯化稀土的成分为：GdCl3、YbCl3、ErCl3，摩尔质量比为：40:9:1。Further, in the step (1), the components of rare earth chloride are: GdCl 3 , YbCl 3 , ErCl 3 , and the molar mass ratio is: 40:9:1.
进一步地，所述步骤（1）中，OA和ODE的用量各为8mL。Further, in the step (1), the dosage of OA and ODE is 8mL each.
进一步地，所述步骤（1）中，氟化钠与稀土的摩尔质量比为：5:1。Further, in the step (1), the molar mass ratio of sodium fluoride to rare earth is: 5:1.
进一步地，所述步骤（1）中，离心分离时离心机转速应设置为8200rpm。Further, in the step (1), the rotational speed of the centrifuge should be set to 8200rpm during centrifugation.
进一步地，所述步骤（2）中，丙酮和环己烷的体积比为：1:1。Further, in the step (2), the volume ratio of acetone and cyclohexane is: 1:1.
进一步地，所述步骤（2）中，搅拌状态下的转速设置为：520rpm。Further, in the step (2), the rotational speed in the stirring state is set to: 520 rpm.
进一步地，所述步骤（3）中，高锰酸钾和高碘酸钠的用量分的质量比为：1:12.5。Further, in the step (3), the mass ratio of the dosage of potassium permanganate and sodium periodate is: 1:12.5.
进一步地，所述步骤（4）中，将烧杯B中的溶液加入到烧杯A中时，必须采用缓慢滴加的方式。Further, in the step (4), when adding the solution in the beaker B to the beaker A, it must be slowly added dropwise.
进一步地，所述步骤（4）中，将烧杯B中的溶液加入到烧杯A中后，搅拌反应时长为24h。Further, in the step (4), after adding the solution in the beaker B to the beaker A, the stirring reaction time is 24h.
进一步地，所述步骤（4）中，将烧杯B中的溶液加入到烧杯A中后，搅拌反应环境温度为23℃。Further, in the step (4), after adding the solution in the beaker B to the beaker A, the temperature of the stirring reaction environment is 23°C.
进一步地，所述步骤（4）中，将烧杯B中的溶液加入到烧杯A中后，搅拌转速应设置为520rpm。Further, in the step (4), after adding the solution in the beaker B to the beaker A, the stirring speed should be set to 520rpm.
进一步地，所述步骤（4）中，离心分离时，离心机转速应设置为：4000rpm。Further, in the step (4), during centrifugation, the rotation speed of the centrifuge should be set to: 4000rpm.
本发明提供了一种基于配体氧化的油酸封端上转换发光纳米颗粒的亲水性修饰方法，通过该方法对上转换发光纳米颗粒做亲水性修饰后，使得原本具有疏水性的上转换发光纳米颗粒具备极其优越的亲水性，从而可在此基础上展开上转换发光纳米颗粒的生物应用。The invention provides a hydrophilic modification method of oleic acid-capped up-conversion luminescent nanoparticles based on ligand oxidation. After the hydrophilic modification of the up-conversion luminescent nanoparticles by the method, the originally hydrophobic on Converted luminescent nanoparticles have extremely superior hydrophilicity, so the biological application of upconverted luminescent nanoparticles can be developed on this basis.
本发明的技术构思为：配体氧化的实现主要是利用高锰酸钾的强氧化性，高锰酸钾将上转换发光纳米颗粒表面的油酸配体氧化成为壬二酸，从而使得油酸封端的疏水性上转换发光纳米颗粒具备亲水性；在此过程中，高锰酸根离子会被还原成为锰酸根离子，而锰酸酸根离子的氧化性相较于高锰酸根离子较弱，因此反应体系中需要加入高碘酸钠从而实现抑制锰酸根离子的形成的同时能够加强高锰酸根离子的重复利用；The technical idea of the present invention is as follows: the realization of ligand oxidation mainly utilizes the strong oxidizing property of potassium permanganate, and potassium permanganate oxidizes the oleic acid ligand on the surface of the up-conversion luminescent nanoparticle to azelaic acid, thereby making oleic acid The capped hydrophobic upconversion luminescent nanoparticles are hydrophilic; in this process, permanganate ions are reduced to manganate ions, and manganate ions are less oxidative than permanganate ions, so It is necessary to add sodium periodate in the reaction system so as to suppress the formation of manganate ions and at the same time strengthen the reuse of permanganate ions;
另外，高猛酸根离子的含量直接决定了整个氧化过程的氧化速度，理论上而言，高锰酸钾用量越大，反应速度越快，但是如果高锰酸钾用量过大，且此时高碘酸钠的含量不足一直锰酸根离子的形成，此时反而会降低上转换发光纳米颗粒表面油酸配体的氧化速度，因此要求体系中高碘酸钠的含量应远远大于高锰酸钾。In addition, the content of permanganate ion directly determines the oxidation speed of the whole oxidation process. In theory, the larger the amount of potassium permanganate, the faster the reaction speed, but if the amount of potassium permanganate is too large, and the high The content of sodium iodate is insufficient to prevent the formation of manganate ions, which will reduce the oxidation rate of oleic acid ligands on the surface of upconversion luminescent nanoparticles. Therefore, the content of sodium periodate in the system should be much larger than that of potassium permanganate.
与现有的技术相比，本发明的有益效果表现在：Compared with the prior art, the beneficial effects of the present invention are shown in:
（1）本发明提供了一种基于配体氧化的油酸封端上转换发光纳米颗粒的亲水性修饰方法，该方法可获得亲水性及其优越的上转换发光纳米颗粒。(1) The present invention provides a hydrophilic modification method of oleic acid-terminated upconversion luminescent nanoparticles based on ligand oxidation, which can obtain hydrophilic and superior upconversion luminescent nanoparticles.
（2）本发明提供了一种基于配体氧化的油酸封端上转换发光纳米颗粒的亲水性修饰方法，相较于常规的配体氧化方法，本发明加大高锰酸钾的用量能大大提升了油酸配体的氧化速度，仅需要氧化24h即可。(2) The present invention provides a hydrophilic modification method of oleic acid-capped up-conversion luminescent nanoparticles based on ligand oxidation. Compared with the conventional ligand oxidation method, the present invention increases the dosage of potassium permanganate. It can greatly improve the oxidation rate of oleic acid ligand, and only needs to be oxidized for 24h.
（3）本发明提供了一种基于配体氧化的油酸封端上转换发光纳米颗粒的亲水性修饰方法，本发明中油酸封端的上转换发光纳米颗粒在氧化前被分散在环己烷和丙酮组成的混合有机溶剂中，相较于常规的配体氧化方法，本发明能够获得颜色较浅的而非棕黑色的上转换发光纳米颗粒水溶液。(3) The present invention provides a hydrophilic modification method of oleic acid-terminated upconversion luminescent nanoparticles based on ligand oxidation. The oleic acid-terminated upconversion luminescent nanoparticles in the present invention are dispersed in cyclohexane before oxidation. In the mixed organic solvent composed of acetone and acetone, compared with the conventional ligand oxidation method, the present invention can obtain an aqueous solution of up-conversion luminescent nanoparticles with lighter color rather than brown-black.
附图说明Description of drawings
图1是配体氧化的油酸封端上转换发光纳米颗粒的亲水性修饰方法的氧化过程。Figure 1 shows the oxidation process of the hydrophilic modification method of ligand-oxidized oleic acid-terminated upconversion luminescent nanoparticles.
图2是油酸封端上转换发光纳米颗粒的投射电镜照片。Figure 2 is a transmission electron microscope photograph of oleic acid-capped upconversion luminescent nanoparticles.
图3是油酸封端上转换发光纳米颗粒经配体氧化后的在水溶液中的发光光谱。Figure 3 is the luminescence spectrum of oleic acid-capped upconversion luminescent nanoparticles in aqueous solution after ligand oxidation.
具体实施方式Detailed ways
以下结合实例对本发明进行详细描述，但本发明不限于这些实施例。The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
实施例1：Example 1:
（1）上转换发光材料的制备：(1) Preparation of up-conversion luminescent materials:
三颈烧瓶中加入0.08mmol GdCl3、0.018mmol YbCl3、0.002mmol ErCl3、8mL ODE，8mL OA，搅拌状态下升温至160℃，反应40min后，降至室温加入0.5mmol氟化钠，室温状态下搅拌20min后升温至310℃，反应30min后，降至室温，离心分离，将0.1g离心物分散在20mL环己烷中，得到纳米颗粒的胶体溶液。0.08mmol GdCl3, 0.018mmol YbCl3, 0.002mmol ErCl3, 8mL ODE, 8mL OA were added to the three-necked flask, and the temperature was raised to 160°C under stirring. Then, the temperature was raised to 310° C., and after the reaction for 30 min, the temperature was lowered to room temperature, and centrifugation was performed, and 0.1 g of the centrifuge was dispersed in 20 mL of cyclohexane to obtain a colloidal solution of nanoparticles.
（2）上转换发光纳米颗粒在混合有机溶剂中分散：(2) Upconversion luminescent nanoparticles are dispersed in mixed organic solvent:
烧杯A中加入步骤（1）中得到的上转换发光纳米颗粒胶体溶液，转速为520rpm的搅拌状态下加入20mL丙酮。The upconversion luminescent nanoparticle colloidal solution obtained in step (1) was added to the beaker A, and 20 mL of acetone was added under stirring at a rotational speed of 520 rpm.
（3）氧化溶液配制：(3) Preparation of oxidation solution:
烧杯B中加入40mg高锰酸钾和500mg高碘酸钠，加入20mL去离子水搅拌至固体完全溶解。Add 40 mg of potassium permanganate and 500 mg of sodium periodate to beaker B, add 20 mL of deionized water, and stir until the solid is completely dissolved.
（4）得到上转换发光纳米颗粒的水溶液：(4) The aqueous solution of upconversion luminescent nanoparticles is obtained:
将烧杯B中的溶液缓慢滴加入烧杯A中，室温下，搅拌24h后，用去离子水洗涤两次，并将离心物分散在10mL去离子水中，得到上转换发光纳米颗粒的水溶液。The solution in beaker B was slowly added dropwise to beaker A, stirred for 24 hours at room temperature, washed twice with deionized water, and the centrifuge was dispersed in 10 mL of deionized water to obtain an aqueous solution of upconversion luminescent nanoparticles.
实施例2：Example 2:
（1）上转换发光材料的制备：(1) Preparation of up-conversion luminescent materials:
三颈烧瓶中加入0.12mmol GdCl3、0.027mmol YbCl3、0.003mmol ErCl3、8mL ODE，8mL OA，搅拌状态下升温至160℃，反应40min后，降至室温加入0.7mmol氟化钠，室温状态下搅拌20min后升温至310℃，反应30min后，降至室温，离心分离，将0.1g离心物分散在40mL环己烷中，得到纳米颗粒的胶体溶液。Add 0.12mmol GdCl3, 0.027mmol YbCl3, 0.003mmol ErCl3, 8mL ODE, 8mL OA to the three-necked flask, heat up to 160°C under stirring, react for 40min, drop to room temperature, add 0.7mmol sodium fluoride, stir at room temperature for 20min Then, the temperature was raised to 310° C., and after the reaction for 30 min, the temperature was lowered to room temperature, and centrifugation was performed, and 0.1 g of the centrifuge was dispersed in 40 mL of cyclohexane to obtain a colloidal solution of nanoparticles.
（2）上转换发光纳米颗粒在混合有机溶剂中分散：(2) Upconversion luminescent nanoparticles are dispersed in mixed organic solvent:
烧杯A中加入步骤（1）中得到的上转换发光纳米颗粒胶体溶液，转速为520rpm的搅拌状态下加入40mL丙酮。The upconversion luminescent nanoparticle colloidal solution obtained in step (1) was added to the beaker A, and 40 mL of acetone was added under stirring at a rotational speed of 520 rpm.
（3）氧化溶液配制：(3) Preparation of oxidation solution:
烧杯B中加入60mg高锰酸钾和750mg高碘酸钠，加入40mL去离子水搅拌至固体完全溶解。Add 60 mg of potassium permanganate and 750 mg of sodium periodate to beaker B, add 40 mL of deionized water, and stir until the solid is completely dissolved.
步骤（4）同实施例1中的步骤（4）。Step (4) is the same as step (4) in Example 1.
实施例3：Example 3:
（1）上转换发光材料的制备：(1) Preparation of up-conversion luminescent materials:
三颈烧瓶中加入0.16mmol GdCl3、0.036mmol YbCl3、0.004mmol ErCl3、8mL ODE，8mL OA，搅拌状态下升温至160℃，反应40min后，降至室温加入1.0mmol氟化钠，室温状态下搅拌20min后升温至310℃，反应30min后，降至室温，离心分离，将0.1g离心物分散在40mL环己烷中，得到纳米颗粒的胶体溶液。0.16mmol GdCl3, 0.036mmol YbCl3, 0.004mmol ErCl3, 8mL ODE, 8mL OA were added to the three-necked flask, and the temperature was raised to 160°C under stirring. Then, the temperature was raised to 310° C., and after the reaction for 30 min, the temperature was lowered to room temperature, and centrifugation was performed, and 0.1 g of the centrifuge was dispersed in 40 mL of cyclohexane to obtain a colloidal solution of nanoparticles.
（2）上转换发光纳米颗粒在混合有机溶剂中分散：(2) Upconversion luminescent nanoparticles are dispersed in mixed organic solvent:
烧杯A中加入步骤（1）中得到的上转换发光纳米颗粒胶体溶液，转速为520rpm的搅拌状态下加入40mL丙酮。The upconversion luminescent nanoparticle colloidal solution obtained in step (1) was added to the beaker A, and 40 mL of acetone was added under stirring at a rotational speed of 520 rpm.
（3）氧化溶液配制：(3) Preparation of oxidation solution:
烧杯B中加入80mg高锰酸钾和1000mg高碘酸钠，加入40mL去离子水搅拌至固体完全溶解。Add 80 mg of potassium permanganate and 1000 mg of sodium periodate to beaker B, add 40 mL of deionized water, and stir until the solid is completely dissolved.
步骤（4）同实施例1中的步骤（4）。Step (4) is the same as step (4) in Example 1.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101121543A (en) * | 2007-08-02 | 2008-02-13 | 复旦大学 | A kind of preparation method of water-soluble rare earth nano material |
| US20140056817A1 (en) * | 2011-05-06 | 2014-02-27 | Sbi Pharmaceuticals Co., Ltd. | Photodynamic therapy or diagnostic agent, using infrared-spectrum light |
| CN105778917A (en) * | 2016-03-16 | 2016-07-20 | 深圳大学 | Core-shell nanometer luminous material and preparation method thereof |
| CN106281327A (en) * | 2016-08-08 | 2017-01-04 | 东南大学 | One class hydrophilic up-conversion and preparation method thereof |
| CN110743013A (en) * | 2019-05-05 | 2020-02-04 | 上海大学 | Up-conversion nano composite material for dual-power cooperative treatment, preparation method and application |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101121543A (en) * | 2007-08-02 | 2008-02-13 | 复旦大学 | A kind of preparation method of water-soluble rare earth nano material |
| US20140056817A1 (en) * | 2011-05-06 | 2014-02-27 | Sbi Pharmaceuticals Co., Ltd. | Photodynamic therapy or diagnostic agent, using infrared-spectrum light |
| CN105778917A (en) * | 2016-03-16 | 2016-07-20 | 深圳大学 | Core-shell nanometer luminous material and preparation method thereof |
| CN106281327A (en) * | 2016-08-08 | 2017-01-04 | 东南大学 | One class hydrophilic up-conversion and preparation method thereof |
| CN110743013A (en) * | 2019-05-05 | 2020-02-04 | 上海大学 | Up-conversion nano composite material for dual-power cooperative treatment, preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| RAFIK NACCACHE，ETC: "Controlled Synthesis and Water Dispersibility of Hexagonal Phase NaGdF4 :Ho3+/Yb3+ Nanoparticles", 《CHEM. MATER. 》 * |
| ZHIGANG CHEN，ETC: "Versatile Synthesis Strategy for Carboxylic Acid-functionalized Upconverting Nanophosphors as Biological Labels", 《J. AM. CHEM. SOC. 》 * |
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