CN102241968A - Method for implementing transfer of up-conversion nanocrystals from oil phase to aqueous phase - Google Patents
Method for implementing transfer of up-conversion nanocrystals from oil phase to aqueous phase Download PDFInfo
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- PSLWZOIUBRXAQW-UHFFFAOYSA-M dimethyl(dioctadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC PSLWZOIUBRXAQW-UHFFFAOYSA-M 0.000 description 1
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Abstract
本发明属于功能性无机纳米晶表面改性技术领域，涉及一种将油溶性上变频纳米晶转移到水相的方法，从而增加了上变频纳米晶的生物兼容性。其是在室温敞开体系中把小分子表面活性剂0.02～0.2g溶解在10ml～20ml水中，再加入溶解在低沸点有机溶剂中的上变频纳米晶溶液1～4ml，加热到55～80度使有机溶剂挥发，从而得到水溶性上变频纳米晶。本发明方法借助小分子表面活性剂与上变频纳米晶表面配体之间的疏水-疏水相互作用，形成稳定的包覆层，实现纳米晶表面从疏水到亲水的改变。该方法简便易行，可根据需要引入不同种类表面活性剂，解决了上变频纳米晶从油相转移到水相的难点，为与生物分子及其他材料的偶联提供反应平台。
The invention belongs to the technical field of surface modification of functional inorganic nanocrystals, and relates to a method for transferring oil-soluble up-conversion nanocrystals to a water phase, thereby increasing the biocompatibility of the up-conversion nanocrystals. It is to dissolve 0.02-0.2g of small molecule surfactant in 10ml-20ml of water in an open system at room temperature, then add 1-4ml of up-converting nanocrystal solution dissolved in a low-boiling point organic solvent, and heat it to 55-80 degrees to make it The organic solvent is volatilized, thereby obtaining the water-soluble up-conversion nanocrystal. The method of the invention utilizes the hydrophobic-hydrophobic interaction between the small-molecule surfactant and the surface ligand of the up-conversion nano-crystal to form a stable coating layer and realize the change of the surface of the nano-crystal from hydrophobic to hydrophilic. The method is simple and easy, and different types of surfactants can be introduced according to the needs, which solves the difficulty of the up-conversion nanocrystals from the oil phase to the water phase, and provides a reaction platform for coupling with biomolecules and other materials.
Description
技术领域 technical field
本发明属于功能性无机纳米晶表面改性技术领域，具体涉及一种将油溶性上变频纳米晶转移到水相的普适方法，从而增加上变频纳米晶的生物兼容性。The invention belongs to the technical field of surface modification of functional inorganic nanocrystals, and in particular relates to a universal method for transferring oil-soluble up-conversion nanocrystals to a water phase, thereby increasing the biocompatibility of the up-conversion nanocrystals.
背景技术 Background technique
上变频纳米晶具有独特的光学性质，能吸收两个或多个低能量光子，激发出一个高能量光子，因此成为新材料研究的一个热点，被应用在诸多基础研究领域中，例如固体激光器、光发射装置、生物探针、生物检验、低密度红外成像等。但现有技术制备出的上变频纳米晶表面被疏水烷基链包覆，只能分散在甲苯、三氯甲烷等非极性溶剂中，实现此类材料的进一步应用、提高与其他材料的兼容，需要进行表面改性。尤其是上变频纳米晶应用在生物体近红外成像时，不会对生物体造成伤害，在生命科学研究中受到越来越多的关注。但生物体一般都是亲水的，与疏水纳米晶不兼容，只有对纳米晶进行表面亲水改性，从油相转移到水相，才能实现在生命科学上的应用。以往方法是用大分子聚合物进行改性，需要在氮气保护条件下控制pH、温度、时间等，方法复杂，而且每种方法的反应条件都不相同，缺乏普适性。探寻普适方法一直是该领域的瓶颈。Up-converting nanocrystals have unique optical properties, can absorb two or more low-energy photons, and excite one high-energy photon, so they have become a hot spot in the research of new materials and are used in many basic research fields, such as solid-state lasers, Light emitting devices, biological probes, biological testing, low-density infrared imaging, etc. However, the surface of the up-converting nanocrystals prepared by the existing technology is covered with hydrophobic alkyl chains, and can only be dispersed in non-polar solvents such as toluene and chloroform, so as to realize the further application of such materials and improve the compatibility with other materials , surface modification is required. In particular, when up-converting nanocrystals are used in near-infrared imaging of organisms, they will not cause harm to organisms, and have received more and more attention in life science research. However, organisms are generally hydrophilic and incompatible with hydrophobic nanocrystals. Only by modifying the surface of nanocrystals to be hydrophilic and transferring them from the oil phase to the water phase can they be applied in life sciences. In the past, macromolecular polymers were used for modification, and pH, temperature, time, etc. need to be controlled under nitrogen protection conditions. The method was complicated, and the reaction conditions of each method were different, which lacked universality. Exploring universal methods has always been the bottleneck in this field.
为了解决这一问题，我们使用各种小分子表面活性剂对上变频纳米晶进行表面亲水改性。该方法普遍适用于阳离子、阴离子及非离子型表面活性剂，能非常简单的将纳米晶转移到水相，同时赋予丰富的表面功能。使用的原料都是商业上直接购买的，是一种适合工业上对上变频纳米晶进行表面亲水处理的有效方法。To address this issue, we used various small-molecule surfactants to modify the surface of upconverting nanocrystals to be hydrophilic. This method is generally applicable to cationic, anionic, and nonionic surfactants, and can transfer nanocrystals to the aqueous phase very simply, while endowing them with rich surface functions. The raw materials used are all directly purchased commercially, and it is an effective method suitable for the industrial surface hydrophilic treatment of the up-converting nanocrystals.
发明内容 Contents of the invention
本发明的目的就是提供一种操作简便、普遍适用的方法，将油溶性上变频纳米晶转移到水相，即直接加入小分子表面活性剂，在相同转移条件下通过使用不同种类表面活性剂获得不同表面功能：使表面带正电荷，负电荷或者中性进一步与无机物比如二氧化硅或者有机物比如聚吡咯反应The purpose of the present invention is to provide a method that is easy to operate and universally applicable to transfer oil-soluble up-conversion nanocrystals to the water phase, that is, directly add small molecule surfactants, and obtain them by using different types of surfactants under the same transfer conditions. Different surface functions: make the surface positively charged, negatively charged or neutral to further react with inorganic substances such as silica or organic substances such as polypyrrole
该方法直接使用各种小分子表面活性剂，借助他们与上变频纳米晶表面配体之间的疏水-疏水相互作用，形成稳定的包覆层，实现纳米晶表面从疏水到亲水的改变。该方法简便易行，可根据需要引入不同种类表面活性剂，解决了上变频纳米晶从油相转移到水相的难点，为与生物分子及其他材料的偶联提供反应平台。This method directly uses various small-molecule surfactants to form a stable coating layer by virtue of the hydrophobic-hydrophobic interaction between them and the surface ligands of the up-converting nanocrystals, and realizes the change of the surface of the nanocrystals from hydrophobic to hydrophilic. The method is simple and easy, and different types of surfactants can be introduced according to the needs, which solves the difficulty of the up-conversion nanocrystals from the oil phase to the water phase, and provides a reaction platform for coupling with biomolecules and other materials.
本发明使用的原料都是商业上直接购买的，不需要进一步处理，按照一定比例直接混合即可，具有良好的实验重复性，同时保持了上变频纳米晶的发光性能，是一种适合工业上对上变频纳米晶进行表面亲水处理的有效方法。The raw materials used in the present invention are all purchased commercially without further treatment, and can be directly mixed according to a certain ratio, which has good experimental repeatability and maintains the luminescence performance of up-converting nanocrystals. It is an industrially suitable An effective method for surface hydrophilic treatment of up-converting nanocrystals.
具体来说，本发明步骤如下：Specifically, the steps of the present invention are as follows:
在室温敞开体系中把小分子表面活性剂0.02～0.2g溶解在10ml～20ml水中，再加入溶解在低沸点有机溶剂中的上变频纳米晶溶液1～4ml，上变频纳米晶与小分子表面活性剂用量的摩尔比为1∶5～15，加热到55～80度使有机溶剂挥发，从而得到水溶性上变频纳米晶。In an open system at room temperature, dissolve 0.02-0.2g of small molecule surfactants in 10ml-20ml of water, then add 1-4ml of up-conversion nanocrystal solution dissolved in a low-boiling point organic solvent, and the up-conversion nanocrystals and small molecule surface active The molar ratio of the agent dosage is 1:5-15, and the organic solvent is volatilized by heating to 55-80 degrees, so as to obtain the water-soluble up-conversion nano crystal.
上述方法中所述的上变频纳米晶可以是NaYF4(Yb，Er)、NaYF4(Yb，Tm)、NaYF4(Yb，Ho)、NaGdF4(Yb，Er)、YF3(Yb，Er)、LaF3(Yb，Tm)、NdF3(Yb，Tm)、GdF3(Yb，Er)、EuF3(Yb，Er)等；低沸点有机溶剂为三氯甲烷、二氯甲烷、甲苯、正己烷、环己烷等；小分子表面活性剂为十二烷基硫酸钠(SDS)、十二烷基苯磺酸钠(SDBS)、九-十八烯酸钠、十八酸钠等阴离子型表面活性剂，十六烷基三甲基溴化铵(CTAB)、十二烷基三甲基溴化铵(DTAB)、二-十八烷基二甲基溴化铵等阳离子型表面活性剂，也可以是聚乙二醇辛基苯基醚(Triton x-100)等非离子型表面活性剂。The up-converting nanocrystals described in the above method can be NaYF 4 (Yb, Er), NaYF 4 (Yb, Tm), NaYF 4 (Yb, Ho), NaGdF 4 (Yb, Er), YF 3 (Yb, Er ), LaF 3 (Yb, Tm), NdF 3 (Yb, Tm), GdF 3 (Yb, Er), EuF 3 (Yb, Er), etc.; low boiling point organic solvents are chloroform, dichloromethane, toluene, n-hexane, cyclohexane, etc.; small molecule surfactants are sodium dodecyl sulfate (SDS), sodium dodecylbenzenesulfonate (SDBS), sodium nona-octadecenoate, sodium octadecanoate and other anions Type surfactants, cationic surfactants such as cetyltrimethylammonium bromide (CTAB), dodecyltrimethylammonium bromide (DTAB), di-octadecyldimethylammonium bromide, etc. Agent, also can be polyethylene glycol octyl phenyl ether (Triton x-100) and other non-ionic surfactants.
附图说明 Description of drawings
图1(a)：上变频纳米晶NaYF4(18％Yb，2％Er)的发光光谱；Figure 1(a): The luminescence spectrum of up-conversion nanocrystalline NaYF 4 (18%Yb, 2%Er);
图1(b)：三氯甲烷相NaYF4(18％Yb，2％Er)的透射电镜照片；Figure 1(b): Transmission electron micrograph of NaYF 4 (18%Yb, 2%Er) in chloroform phase;
图1(c)：用SDS转到水相NaYF4(18％Yb，2％Er)的透射电镜照片；Figure 1(c): Transmission electron micrograph of NaYF 4 (18%Yb, 2%Er) transferred to aqueous phase by SDS;
图1(d)：水相NaYF4(18％Yb，2％Er)外面包覆聚吡咯的透射照片；Figure 1(d): The transmission photo of aqueous phase NaYF 4 (18%Yb, 2%Er) coated with polypyrrole;
图2：用CTAB转到水相NaYF4(18％Yb，2％Er)的透射电镜照片；Figure 2: Transmission electron micrograph of NaYF 4 (18%Yb, 2%Er) transferred to aqueous phase with CTAB;
图3：用DTAB转到水相NaYF4(18％Yb，2％Er)的透射电镜照片；Fig. 3: Transmission electron micrograph of water phase NaYF 4 (18%Yb, 2%Er) transferred with DTAB;
图4：用Triton x-100转到水相NaYF4(18％Yb，2％Er)的透射电镜照片；Figure 4: Transmission electron micrograph of NaYF 4 (18%Yb, 2%Er) transferred to aqueous phase with Triton x-100;
图5(a)：上变频纳米晶NaYF4(18％Yb，2％Tm)的发光光谱；Figure 5(a): The luminescence spectrum of up-conversion nanocrystalline NaYF 4 (18%Yb, 2%Tm);
图5(b)：甲苯相NaYF4(18％Yb，2％Tm)的透射电镜照片；Figure 5(b): Transmission electron micrograph of NaYF 4 (18%Yb, 2%Tm) in toluene phase;
图5(c)：甲苯相纳米晶用SDS转到水相NaYF4(18％Yb，2％Tm)的透射电镜照片；Figure 5(c): Transmission electron micrograph of toluene phase nanocrystals transferred to aqueous phase NaYF 4 (18%Yb, 2%Tm) by SDS;
图6：正己烷相纳米晶用CTAB转到水相NaYF4(18％Yb，2％Tm)的透射电镜照片；Fig. 6: Transmission electron micrograph of n-hexane phase nanocrystal transferred to water phase NaYF 4 (18%Yb, 2%Tm) by CTAB;
图7：环己烷相纳米晶用DTAB转到水相NaYF4(18％Yb，2％Tm)的透射电镜照片；Figure 7: Transmission electron micrograph of cyclohexane phase nanocrystal transferred to water phase NaYF 4 (18%Yb, 2%Tm) with DTAB;
图8：二氯甲烷相纳米晶用Triton x-100转到水相NaYF4(18％Yb，2％Tm)的透射电镜照片；Figure 8: Transmission electron micrograph of dichloromethane phase nanocrystal transferred to aqueous phase NaYF 4 (18%Yb, 2%Tm) with Triton x-100;
具体实施方式 Detailed ways
下面结合实施例对本发明做进一步的阐述，而不是要以此对本发明进行限制。The present invention will be further described below in conjunction with the examples, rather than limiting the present invention.
实施例1Example 1
在10ml水中加入0.04g阴离子型表面活性剂SDS，搅拌后溶解得到无色透明溶液，然后加入2ml浓度为1.9×10-2mol/L的NaYF4(摩尔数18％Yb，2％Er，)的三氯甲烷溶液；加热到70摄氏度使三氯甲烷挥发，冷却到室温，得到无色透明的水相NaYF4(摩尔数18％Yb，2％Er)溶液。如图1(a)所示，给出了上变频纳米晶的发光光谱，证明了纳米晶具有上变频的性质；图1(b)给出了三氯甲烷相中纳米晶的透射电镜照片，从图中看出纳米晶大小均匀，分散性很好；图1(c)给出了水相中纳米晶的透射电镜照片，我们可以看到粒子没有聚集，分散性很好，证明了油相的纳米晶被成功转到了水相；利用SDS所带负电与吡咯氨基所带的正电相互作用，在纳米晶周围包覆了一层壳层，图1(d)给出了进一步对水相纳米晶用聚吡咯进行表面生物兼容性修饰后的透射照片，进一步证明了油相纳米晶被转到了水相，利用表面的电荷还能与吡咯进行相互作用。Add 0.04g of anionic surfactant SDS in 10ml of water, dissolve after stirring to obtain a colorless transparent solution, then add 2ml of NaYF with a concentration of 1.9×10 -2 mol/L (mole number 18% Yb, 2% Er,) Chloroform solution; heated to 70 degrees Celsius to volatilize the chloroform, and cooled to room temperature to obtain a colorless and transparent aqueous NaYF 4 (mole number 18% Yb, 2% Er) solution. As shown in Figure 1(a), the luminescence spectrum of the up-converting nanocrystal is given, which proves that the nanocrystal has the property of up-converting; Figure 1(b) shows the transmission electron microscope photo of the nanocrystal in the chloroform phase, It can be seen from the figure that the size of the nanocrystals is uniform and the dispersion is very good; Figure 1(c) shows the TEM photo of the nanocrystals in the water phase, we can see that the particles are not aggregated and the dispersion is very good, which proves that the oil phase The nanocrystals were successfully transferred to the water phase; using the interaction between the negative charge of SDS and the positive charge of the pyrrole amino group, a shell was coated around the nanocrystals. Figure 1(d) shows the further improvement of the water phase The transmission photos of nanocrystals modified with polypyrrole for surface biocompatibility further prove that the oil phase nanocrystals have been transferred to the water phase, and the surface charges can also interact with pyrrole.
实施例2Example 2
在10ml水中加入0.04g阳离子表面活性剂CTAB，搅拌后溶解得到无色透明溶液，加入2ml浓度为1.9×10-2mol/L的NaYF4(摩尔数18％Yb，2％Er)三氯甲烷溶液；加热到70摄氏度使三氯甲烷挥发，冷却到室温，得到无色透明的水相NaYF4(摩尔数18％Yb，2％Er)溶液。如图1(b)所示，给出了三氯甲烷相中纳米晶的透射电镜照片，图2给出了水相中纳米晶的透射电镜照片，我们可以看到粒子没有聚集，分散性很好，证明了油相的纳米晶被成功转到了水相。Add 0.04g of cationic surfactant CTAB in 10ml of water, dissolve after stirring to obtain a colorless transparent solution, add 2ml of NaYF 4 (mol number 18%Yb, 2%Er) trichloromethane with a concentration of 1.9×10 -2 mol/L Solution; heated to 70 degrees Celsius to volatilize the chloroform, cooled to room temperature to obtain a colorless and transparent aqueous NaYF 4 (mole number 18% Yb, 2% Er) solution. As shown in Figure 1(b), the TEM photo of the nanocrystals in the chloroform phase is given, and Figure 2 shows the TEM photo of the nanocrystals in the water phase, we can see that the particles are not aggregated, and the dispersion is very good Well, it proved that the nanocrystals in the oil phase were successfully transferred to the water phase.
实施例3Example 3
在10ml水中加入0.04g阳离子表面活性剂DTAB，搅拌后溶解得到无色透明溶液，加入2ml浓度为1.9×10-2mol/L的NaYF4(摩尔数18％Yb，2％Er)三氯甲烷溶液；加热到70摄氏度使三氯甲烷挥发，冷却到室温，得到无色透明的水相NaYF4(摩尔数18％Yb，2％Er)溶液。如图1(b)所示，给出了三氯甲烷相中纳米晶的透射电镜照片，图3给出了水相中纳米晶的透射电镜照片，我们可以看到粒子没有聚集，分散性很好，证明了油相的纳米晶被成功转到了水相。Add 0.04g of cationic surfactant DTAB in 10ml of water, dissolve after stirring to obtain a colorless transparent solution, add 2ml of NaYF 4 (mol number 18%Yb, 2%Er) trichloromethane with a concentration of 1.9×10 -2 mol/L Solution; heated to 70 degrees Celsius to volatilize the chloroform, cooled to room temperature, to obtain a colorless and transparent aqueous NaYF4 (mol number 18% Yb, 2% Er) solution. As shown in Figure 1(b), the TEM photo of the nanocrystals in the chloroform phase is given, and Figure 3 shows the TEM photo of the nanocrystals in the water phase, we can see that the particles are not aggregated, and the dispersion is very good Well, it proved that the nanocrystals in the oil phase were successfully transferred to the water phase.
实施例4Example 4
在10ml水中加入0.04g非离子型表面活性剂Triton x-100，搅拌后溶解得到无色透明溶液，加入2ml浓度为1.9×10-2mol/L的NaYF4(摩尔数18％Yb，2％Er)三氯甲烷溶液；加热到70摄氏度使三氯甲烷挥发，冷却到室温，得到无色透明的水相NaYF4(摩尔数18％Yb，2％Er)溶液。如图1(b)所示，给出了三氯甲烷相中纳米晶的透射电镜照片，图4给出了水相中纳米晶的透射电镜照片，我们可以看到粒子没有聚集，分散性很好，证明了油相的纳米晶被成功转到了水相。Add 0.04g nonionic surfactant Triton x-100 in 10ml water, dissolve after stirring to obtain a colorless transparent solution, add 2ml concentration and be 1.9×10 -2 mol/L NaYF 4 (mol number 18%Yb, 2% Er) Chloroform solution; heated to 70 degrees Celsius to volatilize the chloroform, cooled to room temperature to obtain a colorless and transparent aqueous NaYF4 (18% Yb in moles, 2% Er) solution. As shown in Figure 1(b), the TEM photo of the nanocrystals in the chloroform phase is given, and Figure 4 shows the TEM photo of the nanocrystals in the water phase, we can see that the particles are not aggregated, and the dispersion is very good Well, it proved that the nanocrystals in the oil phase were successfully transferred to the water phase.
实施例5Example 5
在10ml水中加入0.04g阴离子表面活性剂SDS，搅拌后溶解得到无色透明溶液，加入2ml浓度为1.9×10-2mol/L的NaYF4(摩尔数18％Yb，2％Tm)甲苯溶液；加热到55摄氏度使甲苯挥发，冷却到室温，得到无色透明的水相NaYF4(摩尔数18％Yb，2％Tm)溶液。如图5(a)所示，给出了上变频纳米晶的发光光谱，证明了纳米晶具有上变频的性质；图5(b)给出了甲苯相中纳米晶的透射电镜照片，从图中看出纳米晶大小均匀，分散性很好；图5(c)给出了水相中纳米晶的透射电镜照片，我们可以看到粒子没有聚集，分散性很好，证明了油相的纳米晶被成功转到了水相。Add 0.04g of anionic surfactant SDS to 10ml of water, dissolve after stirring to obtain a colorless and transparent solution, add 2ml of NaYF 4 (mole number 18%Yb, 2%Tm) toluene solution with a concentration of 1.9×10 -2 mol/L; Heat to 55°C to volatilize the toluene, and cool to room temperature to obtain a colorless and transparent aqueous NaYF 4 (mole number 18% Yb, 2% Tm) solution. As shown in Figure 5(a), the luminescence spectrum of the up-conversion nanocrystal is given, which proves that the nanocrystal has the property of up-conversion; Figure 5(b) shows the TEM photo of the nanocrystal in the toluene phase, from the figure It can be seen that the size of the nanocrystals is uniform and the dispersion is very good; Figure 5(c) shows the TEM photo of the nanocrystals in the water phase. We can see that the particles are not aggregated and the dispersion is very good, which proves the nanocrystals in the oil phase. The crystals were successfully transferred to the aqueous phase.
实施例6Example 6
在10ml水中加入0.04g阳离子表面活性剂CTAB，搅拌后溶解得到无色透明溶液，加入2ml浓度为1.9×10-2mol/L的NaYF4(摩尔数18％Yb，2％Tm)正己烷溶液；加热到65摄氏度使正己烷挥发，冷却到室温，得到无色透明的水相NaYF4(摩尔数18％Yb，2％Tm)溶液。如图5(a)所示，给出了正己烷相中纳米晶的透射电镜照片，图6给出了水相中纳米晶的透射电镜照片，我们可以看到粒子没有聚集，分散性很好，证明了油相的纳米晶被成功转到了水相。Add 0.04g of cationic surfactant CTAB in 10ml of water, dissolve after stirring to obtain a colorless transparent solution, add 2ml of NaYF 4 (mol number 18%Yb, 2%Tm) n-hexane solution with a concentration of 1.9×10 -2 mol/L ; Heated to 65 degrees Celsius to volatilize n-hexane, cooled to room temperature, and obtained a colorless and transparent aqueous NaYF 4 (mole number 18% Yb, 2% Tm) solution. As shown in Figure 5(a), the TEM photo of the nanocrystals in the n-hexane phase is given, and Figure 6 shows the TEM photo of the nanocrystals in the water phase, we can see that the particles are not aggregated, and the dispersion is very good , proving that the nanocrystals in the oil phase were successfully transferred to the water phase.
实施例7Example 7
在10ml水中加入0.04g阳离子表面活性剂DTAB，搅拌后溶解得到无色透明溶液，加入2ml浓度为1.9×10-2mol/L的NaYF4(摩尔数18％Yb，2％Tm)环己烷溶液；加热到75摄氏度使环己烷挥发，冷却到室温，得到无色透明的水相NaYF4(摩尔数18％Yb，2％Tm)溶液。如图5(a)所示，给出了环己烷相中纳米晶的透射电镜照片，图7给出了水相中纳米晶的透射电镜照片，我们可以看到粒子没有聚集，分散性很好，证明了油相的纳米晶被成功转到了水相。Add 0.04g of cationic surfactant DTAB in 10ml of water, dissolve after stirring to obtain a colorless transparent solution, add 2ml of NaYF 4 (mol number 18%Yb, 2%Tm) cyclohexane with a concentration of 1.9×10 -2 mol/L Solution; heated to 75 degrees Celsius to volatilize cyclohexane, cooled to room temperature to obtain a colorless and transparent aqueous NaYF 4 (mole number 18% Yb, 2% Tm) solution. As shown in Figure 5(a), the TEM photo of the nanocrystals in the cyclohexane phase is given, and Figure 7 shows the TEM photo of the nanocrystals in the water phase, we can see that the particles are not aggregated, and the dispersion is very good Well, it proved that the nanocrystals in the oil phase were successfully transferred to the water phase.
实施例8Example 8
在10ml水中加入0.04g非离子型表面活性剂Triton x-100，搅拌后溶解得到无色透明溶液，加入2ml浓度为1.9×10-2mol/L的NaYF4(摩尔数18％Yb，2％Tm)二氯甲烷溶液；加热到80摄氏度使二氯甲烷挥发，冷却到室温，得到无色透明的水相NaYF4(摩尔数18％Yb，2％Tm)溶液。如图5(a)所示，给出了二氯甲烷相中纳米晶的透射电镜照片，图8给出了水相中纳米晶的透射电镜照片，我们可以看到粒子没有聚集，分散性很好，证明了油相的纳米晶被成功转到了水相。Add 0.04g nonionic surfactant Triton x-100 in 10ml water, dissolve after stirring to obtain a colorless transparent solution, add 2ml concentration and be 1.9×10 -2 mol/L NaYF 4 (mol number 18%Yb, 2% Tm) dichloromethane solution; heated to 80 degrees Celsius to volatilize the dichloromethane, cooled to room temperature to obtain a colorless and transparent aqueous NaYF 4 (mole number 18% Yb, 2% Tm) solution. As shown in Figure 5(a), the TEM photo of the nanocrystals in the dichloromethane phase is given, and Figure 8 shows the TEM photo of the nanocrystals in the water phase, we can see that the particles are not aggregated, and the dispersion is very good Well, it proved that the nanocrystals in the oil phase were successfully transferred to the water phase.
实施例9Example 9
在10ml水中加入0.04g阴离子型表面活性剂SDS，搅拌后溶解得到无色透明溶液，加入2ml浓度为1.9×10-2mol/L的YF3(摩尔数18％Yb，2％Tm)三氯甲烷溶液；加热到70摄氏度使三氯甲烷挥发，冷却到室温，得到无色透明的水相YF3(摩尔数18％Yb，2％Tm)溶液。粒子也是没有聚集，分散性很好。Add 0.04g of anionic surfactant SDS to 10ml of water, dissolve after stirring to obtain a colorless transparent solution, add 2ml of YF 3 (mole number 18 %Yb, 2%Tm) trichloro Methane solution; heating to 70 degrees Celsius to volatilize the chloroform, cooling to room temperature to obtain a colorless and transparent aqueous YF 3 (mole number 18% Yb, 2% Tm) solution. The particles are not aggregated, and the dispersion is very good.
实施例10Example 10
在10ml水中加入0.04g非离子型表面活性剂Triton x-100，搅拌后溶解得到无色透明溶液，加入2ml浓度为1.9×10-2mol/L的LaF3(摩尔数18％Yb，2％Er)甲苯溶液；加热到60摄氏度使甲苯挥发，冷却到室温，得到无色透明的水相LaF3(摩尔数18％Yb，2％Er)溶液。粒子也是没有聚集，分散性很好。Add 0.04g nonionic surfactant Triton x-100 in 10ml water, dissolve after stirring to obtain a colorless transparent solution, add 2ml concentration and be 1.9×10 -2 mol/L LaF 3 (mol number 18%Yb, 2% Er) Toluene solution; heated to 60 degrees Celsius to volatilize the toluene, cooled to room temperature to obtain a colorless and transparent aqueous LaF 3 (mole number 18% Yb, 2% Er) solution. The particles are not aggregated, and the dispersion is very good.
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| CN103374346A (en) * | 2012-04-13 | 2013-10-30 | 中国科学院高能物理研究所 | Method for improving water solubility of nanomaterial through surface modification and nanomaterial modified by method |
| CN106085432A (en) * | 2016-06-07 | 2016-11-09 | 中国科学院合肥物质科学研究院 | Organic-inorganic hybrid nanometer powder body of praseodymium doped lanthanum fluoride and its production and use |
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| CN101735816A (en) * | 2009-12-14 | 2010-06-16 | 孙家跃 | Dual mode luminous rare earth doped cerium fluoride nano crystal, preparation method and surface modification method thereof |
| CN101948694A (en) * | 2010-09-08 | 2011-01-19 | 吉林大学 | Rare earth upconversion nano crystal/silver difunctional composite nano material, preparation method thereof and application thereof in cancer detection and treatment |
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| CN101735816A (en) * | 2009-12-14 | 2010-06-16 | 孙家跃 | Dual mode luminous rare earth doped cerium fluoride nano crystal, preparation method and surface modification method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103127744A (en) * | 2011-11-28 | 2013-06-05 | 中国科学院金属研究所 | Method for transferring nano-particles from oil phase into aqueous phase |
| CN103127744B (en) * | 2011-11-28 | 2014-12-10 | 中国科学院金属研究所 | Method for transferring nano-particles from oil phase into aqueous phase |
| CN103374346A (en) * | 2012-04-13 | 2013-10-30 | 中国科学院高能物理研究所 | Method for improving water solubility of nanomaterial through surface modification and nanomaterial modified by method |
| CN106085432A (en) * | 2016-06-07 | 2016-11-09 | 中国科学院合肥物质科学研究院 | Organic-inorganic hybrid nanometer powder body of praseodymium doped lanthanum fluoride and its production and use |
| CN106085432B (en) * | 2016-06-07 | 2018-04-20 | 中国科学院合肥物质科学研究院 | Organic-inorganic hybrid nanometer powder of praseodymium doped lanthanum fluoride and its preparation method and application |
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