A triethanolamine-modified platinum nanoparticle and its application

Abstract

A triethanolamine-modified platinum nanoparticle and its application, wherein the platinum source of the particle is chloroplatinic acid and / or chloroplatinic acid hydrate, and the particle is prepared in a water solvent by a heating reflux method. The present invention also includes the application of the triethanolamine-modified platinum nanoparticle. The triethanolamine-modified platinum nanoparticle of the present invention has a consistent particle size, uniform morphology, and good dispersibility; the preparation method is simple, the equipment requirements are low, and it is green and environmentally friendly; it can be applied to an electrochemiluminescent immunosensor.

Description

Technical Field

[0001] The invention relates to platinum particles and applications thereof, and in particular to triethanolamine-modified platinum particles and applications thereof. Background Art

[0002] In recent years, metal nanoparticles have become increasingly important, and the research and application of nanometal materials have attracted more and more attention at home and abroad. Metal particles that have at least one dimension at the nanoscale in three-dimensional space or are composed of these nanoscale as basic units are nanometal particles. At the end of the twentieth century, German scientist H. Gleiter first proposed the concept of nanocrystalline particles (Feng T. et al. 2016, Schaefer et al. 1988, Trapp et al. 1995), and first experimentally produced nanoparticles of metals such as silver, copper, and aluminum, which attracted great attention at home and abroad. Nanometal particles are a typical type of nanoparticles. In addition to the common properties of nanoparticles, nanometal particles also have their own unique physical and chemical properties. Therefore, since the advent of metal nanoparticles, the important achievements and application value of metal nanoparticles to society have always attracted attention. Nanometal particles are extremely widely used, and size quantization can occur in this nanosize range. The physical and chemical properties are surprisingly different from those of bulk materials. It is found that metal nanoparticles have more and more powerful properties than traditional bulk metals, which has attracted the attention of a large number of scientific researchers. In order to develop this size quantization, there has been an increasing amount of research on the preparation, characterization and application of nanomaterials in recent years. In order to obtain nanoparticles, the reduction of metal compounds usually requires high temperature, reducing agents and supersaturated conditions. However, traditional methods for preparing nanometal particles are basically physical or chemical methods.

[0003] Platinum metal nanoparticles are a common type of nanometal particles. An increasing number of researchers around the world have conducted a series of synthetic studies on platinum metal nanoparticles. Nowadays, new methods for synthesizing platinum metal nanoparticles are increasingly sought after by scientists. Platinum metal nanomaterials have a wide range of chemical and physical properties and can be used in many technological applications. For example, platinum metal nanoparticles have attracted much attention due to their catalytic activity, electrochemical applications, chemical sensing, and optical properties related to surface plasmon resonance (SPR) occurring in the ultraviolet range of the electromagnetic spectrum (Feng DFet al. 2019, Jiangand Wang 2019, Mangrulkar et al. 2014). The methods for synthesizing platinum metal nanoparticles include sonochemical reduction, biosynthesis, aqueous synthesis, deposition, sol-gel method, etc., and the synthesis methods are relatively complex. The modification of platinum metal nanoparticles also needs further study. Summary of the invention

[0004] The technical problem to be solved by the present invention is to overcome the above-mentioned defects of the prior art and provide a triethanolamine-modified platinum nanoparticle with a simple synthesis method and low cost and its application.

[0005] The technical solution adopted by the present invention to solve the technical problem is as follows: a triethanolamine-modified platinum nanoparticle, the platinum source is chloroplatinic acid and / or chloroplatinic acid hydrate, prepared in a water solvent by a heating reflux method. Triethanolamine is represented by TEOA, and the obtained material is represented by TEOA@PtNPs.

[0006] Preferably, the preparation method is: heating a water-containing reaction container with a reflux device to the reflux temperature, adding a triethanolamine solution, and then dropwise adding a solution of chloroplatinic acid and / or chloroplatinic acid hydrate, heating and reflux reaction, thereby obtaining the product.

[0007] Preferably, the reflux temperature is 100-200°C, more preferably 120-180°C.

[0008] Preferably, the heating reflux reaction time is 2.5 to 4 hours.

[0009] Preferably, the molar ratio of triethanolamine to platinum element added to the reaction container is 20 to 80:1, more preferably 30 to 60:1.

[0010] Preferably, the concentration of the triethanolamine solution is 0.04-0.15 mol / L.

[0011] Preferably, the ratio of the volume of the added triethanolamine solution to the total volume of the reaction solvent is 1:3-10.

[0012] The invention discloses an application of triethanolamine-modified platinum nanoparticles in an electrochemiluminescent immunosensor.

[0013] Preferably, the electrochemiluminescent immunosensor is used to detect SARS virus.

[0014] Preferably, a three-electrode system is used for detection: the working electrode is a short glassy carbon electrode modified with triethanolamine-modified platinum nanoparticles, the counter electrode is a platinum wire electrode, and the reference electrode is a silver / silver chloride electrode.

[0015] Beneficial effects of the present invention:

[0016] (1) The platinum nanoparticles modified with triethanolamine of the present invention have uniform particle size, uniform morphology and good dispersibility;

[0017] (2) The preparation method of TEOA@PtNPs particles is simple, requires low equipment, and is green and environmentally friendly;

[0018] (3)TEOA@PtNPs particles can be used in electrochemiluminescent immunosensors. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 is the TEM image of TEOA@PtNPs particles of Example 1.

[0020] Figure 2 is the TEM image of TEOA@PtNPs particles of Example 2.

[0021] Figure 3 is the TEM image of TEOA@PtNPs particles of Example 3.

[0022] Figure 4 is the TEM image of TEOA@PtNPs particles of Example 4.

[0023] Figure 5 is the TEM image of TEOA@PtNPs particles of Example 5.

[0024] Figure 6 is the TEM image of TEOA@PtNPs particles of Example 6.

[0025] Figure 7 is the TEM image of TEOA@PtNPs particles of Example 7.

[0026] Figure 8 is the TEM image of TEOA@PtNPs particles of Example 8.

[0027] Fig. 9 is the TEM image of TEOA@PtNPs particles of Example 9.

[0028] Fig.10 is the TEM image of TEOA@PtNPs particles of Example 10.

[0029] Fig.11 is the TEM image of TEOA@PtNPs particles of Example 11.

[0030] Fig.12 is the TEM image of TEOA@PtNPs particles of Example 12.

[0031] Fig.13 This is a schematic diagram of the ECL device used in Example 1, wherein: 1-electrochemiluminescence workstation, 2-electrolyte solution, 3-working electrode, 4-reference electrode, 5-comparison electrode, 6-thin layer electrode modified with TEOA@PtNPs particles.

[0032] Fig.14 It is a signal intensity diagram of different SARS antigen concentrations detected by ECL in Example 1. DETAILED DESCRIPTION

[0033] The present invention is further described below in conjunction with the examples and drawings, but the present invention is not limited to the following examples. The methods are conventional methods unless otherwise specified. The raw materials can be obtained from public commercial channels unless otherwise specified.

[0034] Example 1

[0035] In this example, the triethanolamine-modified platinum nanoparticles were prepared in water solvent by heating reflux method, with the platinum source being H2PtCl6·6H2O. The obtained material is denoted as TEOA@PtNPs.

[0036] Instrument pretreatment and reaction solution configuration:

[0037] Prepare aqua regia by mixing concentrated hydrochloric acid and concentrated nitric acid in a volume ratio of 3:1. Soak all glassware in the aqua regia, rinse them with ultrapure water, seal them with plastic wrap and set aside.

[0038] Prepare a TEOA solution with a molar concentration of 0.075 mol / L: add 1 mL of 98% pure TEOA (7.5 mol / L) into a 100 mL clean volumetric flask, dilute to the 100 mL mark, shake to mix evenly to obtain a 0.075 mol / L TEOA solution, and keep in a refrigerator at 4°C for later use.

[0039] Prepare a H2PtCl6·6H2O solution with a mass concentration of 0.04 g / mL: dissolve 1 g H2PtCl6·6H2O in a 10 mL small beaker, add the diluted solution to a clean 25 mL volumetric flask, and shake to mix well to obtain a 0.04 g / mL H2PtCl6·6H2O solution.

[0040] Preparation of triethanolamine-modified platinum nanoparticles:

[0041] A 100mL round-bottom flask with a reflux device and 17.5mL ultrapure water was heated to 140°C in an oil bath (the oil in the oil bath was dimethyl silicone oil, which could withstand a high temperature of 250°C and had a viscosity of 1000mPa.s), 2.04mL of 0.075mol / L TEOA solution was added, and then 100μL of 0.04g / mL H2PtCl6·6H2O solution was added dropwise (the molar ratio of TEOA and H2PtCl6·6H2O was 20:1), and the mixture was heated at 140°C for 3h to obtain TEOA@PtNPs particles. The morphology of the obtained TEOA@PtNPs particles is as follows: Figure 1 shown.

[0042] Application of triethanolamine-modified platinum nanoparticles in electrochemiluminescent immunosensor in this example:

[0043] (1) Polishing, cleaning and characterization of glassy carbon electrodes: The glassy carbon electrodes were polished in 0.5 and 0.05 nm alumina suspensions, and then the electrode surface was thoroughly cleaned with ultrapure water. Then, ultrapure water, anhydrous ethanol, and ultrapure water were used for ultrasonic treatment for 3 min to remove the residual alumina powder on the electrode surface. Then, electrochemical cleaning was used to completely remove the contaminants on the electrode surface. The electrochemical cleaning steps were: in 10 mL 0.50 mol / L H2SO4, the potential range was -1.0 to 1.0 V and the scanning rate was 0.1 V / s. Cyclic voltammetry scanning was performed until stability. The treated glassy carbon electrode was rinsed with a large amount of water and then dried with nitrogen. Finally, the glassy carbon electrode was characterized to detect whether the polishing and cleaning of the glassy carbon electrode met the requirements of the drop material. The electrochemical characterization steps were: in 10 mL 0.50 mol / L K3Fe(CN)6 solution, the potential range was -0.1 to 0.5 V and the scanning rate was 0.05 V / s, and the scanning rate was 3 cycles. The treated glassy carbon electrode was rinsed with plenty of water and then blown dry with nitrogen.

[0044] (2) Electrochemiluminescence detection process. A three-electrode system (working electrode is a short glassy carbon electrode modified with TEOA@PtNPs, counter electrode is a platinum wire electrode, and reference electrode is a silver / silver chloride (Ag / AgCl) electrode) was used to mix 10 mL of 100 mM Ru(bpy)3 2+ A 0.1M PBS (pH 7.0) electrolyte solution was added to the electrolytic cell. The detection conditions were: scanning interval 0-1.35V (vs. Ag / AgCl), scanning speed 0.1V / s, and the photomultiplier tube PMT was set to 800V. The electrochemiluminescence signal on the working electrode was obtained, thereby indirectly obtaining the electrochemiluminescence signal of the TEOA@PtNPs nanomaterial.

[0045] The construction of ECL immunosensor Fig.13 As shown in Figure 2, when used to detect SARS virus, the ECL signal gradually weakens as the concentration of SARS antigen increases. The linear range is 10fg / mL to 10ng / mL, and the detection limit is 4.18fg / mL. Fig.14 shown.

[0046] Embodiments 2 to 6

[0047] Examples 2 to 6 are triethanolamine-modified platinum nanoparticles, where the platinum source is H2PtCl6·6H2O, prepared in an aqueous solvent by heating reflux method. The preparation method of triethanolamine-modified platinum nanoparticles is basically the same as that of Example 1, except that the molar ratio of TEOA and H2PtCl6·6H2O is changed by increasing the amount of TEOA solution: the amounts of TEOA solution used in Examples 2 to 6 are 3.06mL, 4.08mL, 5.1mL, 6.12mL, and 8.16mL, respectively, and the corresponding molar ratios of TEOA and H2PtCl6·6H2O are 30:1, 40:1, 50:1, 60:1, and 80:1, respectively. The morphologies of the resulting TEOA@PtNPs particles are as follows: Figures 2 to 6 shown.

[0048] from Figures 1 to 6 It can be seen that the TEOA@PtNPs prepared in Examples 1 to 6 are almost spherical, and the ratio of the amount of TEOA to H2PtCl6·6H2O has little effect on the diameter of the particles, with an average diameter of 2.2 nm. Figure 1 ), the synthesized TEOA@PtNPs particles are relatively agglomerated, and when the amount of TEOA is large ( Figure 6 ), the shape and diameter of the synthesized TEOA@PtNPs particles are slightly more heterogeneous. When the amount of substance is 50:1 ( Figure 4 ), the synthesized TEOA@PtNPs particles are well dispersed, and their shape and diameter are relatively stable.

[0049] Example 7

[0050] In this example, the triethanolamine-modified platinum nanoparticles were prepared in water solvent by heating reflux method, with the platinum source being H2PtCl6·6H2O. The obtained material is denoted as TEOA@PtNPs.

[0051] Instrument pretreatment and reaction solution configuration: same as Example 1.

[0052] Preparation of triethanolamine-modified platinum nanoparticles:

[0053] A 100mL round-bottom flask with a reflux device and 17.5mL ultrapure water was heated to 100°C in an oil bath (the oil in the oil bath was dimethyl silicone oil, which could withstand a high temperature of 250°C and had a viscosity of 1000mPa.s), 5.1mL of 0.075mol / L TEOA solution was added, and then 100μL of 0.04g / mL H2PtCl6·6H2O solution was added dropwise (the molar ratio of TEOA and H2PtCl6·6H2O was 50:1), and the mixture was heated at 100°C for 3h to obtain TEOA@PtNPs particles. The morphology of the obtained TEOA@PtNPs particles is as follows: Figure 7 shown.

[0054] Embodiments 8 to 12

[0055] Examples 8-12: Triethanolamine-modified platinum nanoparticles, the platinum source is H2PtCl6·6H2O, prepared in water solvent by heating reflux method. The preparation method of triethanolamine-modified platinum nanoparticles is basically the same as that of Example 7, except that the reflux temperatures in Examples 8-12 are 120°C, 140°C, 160°C, 180°C, and 200°C, respectively. The morphologies of the obtained TEOA@PtNPs particles are as follows: Figures 8 to 12 shown.

[0056] from Figures 7 to 12 It can be seen that the prepared TEOA@PtNPs particles are almost spherical, and the temperature has little effect on the diameter of the particles. When the temperature is 100℃, the shape of the synthesized TEOA@PtNPs particles is uneven ( Figure 7 ), when the temperature is 200℃, the agglomeration of the synthesized particles is more serious ( Fig.12 ), Figures 8 to 11 The TEOA@PtNPs particles are dispersed relatively evenly.

Claims

1. A triethanolamine-modified platinum nanoparticle, characterized in that: The platinum source is chloroplatinic acid and / or chloroplatinic acid hydrate, which is prepared in a water solvent by a heating reflux method; The preparation method comprises the following steps: heating a water-containing reaction container with a reflux device to a reflux temperature, adding a triethanolamine solution, then dropwise adding a solution of chloroplatinic acid and / or chloroplatinic acid hydrate, and heating for reflux reaction to obtain the product.

2. The triethanolamine-modified platinum nanoparticles according to claim 1, characterized in that The reflux temperature is 100-200°C.

3. The triethanolamine-modified platinum nanoparticles according to claim 2, characterized in that The heating reflux reaction time is 2.5 to 4 hours.

4. The triethanolamine-modified platinum nanoparticles according to any one of claims 1 to 3, characterized in that: The molar ratio of triethanolamine to platinum element added to the reaction container is 20-80:

1.

5. The triethanolamine-modified platinum nanoparticles according to any one of claims 1 to 3, characterized in that The concentration of the triethanolamine solution is 0.04-0.15 mol / L.

6. The triethanolamine-modified platinum nanoparticles according to any one of claims 1 to 3, characterized in that: The ratio of the volume of the added triethanolamine solution to the total volume of the reaction solvent is 1:3-10.

7. Use of the triethanolamine-modified platinum nanoparticles according to any one of claims 1 to 3 in the preparation of an electrochemiluminescent immunosensor.

8. The use of triethanolamine-modified platinum nanoparticles according to claim 7, characterized in that: The electrochemiluminescent immunosensor is used for detecting SARS virus in an in vitro sample.

9. The use of triethanolamine-modified platinum nanoparticles according to claim 8, characterized in that: A three-electrode system was used for detection: the working electrode was a short glassy carbon electrode modified with triethanolamine-modified platinum nanoparticles, the counter electrode was a platinum wire electrode, and the reference electrode was a silver / silver chloride electrode.

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