CN115161007B - Excitation orthogonal rare earth up-conversion nano probe for trinitrotoluene real-time visual detection, preparation method and application thereof - Google Patents
Excitation orthogonal rare earth up-conversion nano probe for trinitrotoluene real-time visual detection, preparation method and application thereof Download PDFInfo
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Abstract
An excited orthogonal rare earth up-conversion nano probe for trinitrotoluene (TNT) real-time visual detection, a preparation method and application thereof belong to the technical field of luminescent materials. The invention develops a OUCNPs (NaErF 4@NaLuF4@NaYF4:20％Yb,2％Er@NaLuF4) fluorescent probe with a relatively simple structure, wherein 100% of high-concentration Er 3+ in NaErF 4 cores is doped, and the fluorescent probe shows near-monochromatic red emission under 808nm laser excitation; under 980nm laser excitation, a dark green emission was shown. The OUCNPs@PEI self-reference fluorescent probe prepared by the invention can quantitatively analyze TNT in a solution, and the detection limit is 3.04 mu M; the TNT test paper is prepared into test paper, can realize in-situ instant detection of TNT and simultaneously carry out imaging display, is beneficial to on-site screening, and has very broad application prospect.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to an excitation orthogonal rare earth up-conversion nano probe for trinitrotoluene (TNT) instant visual detection doped in a luminescent center sub-structure region, a preparation method and application thereof.
Background
With the rapid development of nanoscience and nanotechnology, the design of a variety of stimuli-responsive nano-platforms for display, information storage, chemical sensing, biomedical and other applications has attracted much attention and interest. The light has the characteristics of rapidness, accuracy, remoteness, space-time controllability and the like in different environments, so that the light has advantages over electromagnetic fields, temperatures, pH values, chemical reactions and other stimuli. Photon up-conversion is a powerful means of converting low energy photons into high energy photons (e.g., from Near Infrared (NIR) to visible light emission). As an ideal candidate for up-conversion, lanthanide ions have unique electronic configurations and rich stepped energy level structures that enable them to produce up-converted luminescence emission spectra under NIR excitation that cover the ultraviolet, visible and near infrared regions. The up-conversion emission has the characteristics of larger anti-Stokes displacement, narrower emission band, longer fluorescence lifetime, good photochemical stability, lower autofluorescence, low toxicity and the like, so that the up-conversion emission has wide application prospect in the fields of imaging, optogenetics, photodynamic therapy, drug controlled release and the like. In particular, excitation-emission orthogonal up-conversion luminescence has recently been achieved in some specially designed nanostructures based on the property that the sensitizers Nd 3+ and Yb 3+ can be excited at 808nm and 980nm, respectively. Orthogonal luminescence means that the corresponding response can be given according to the change of the external stimulus, whereas conventional up-conversion materials can only give a single response under excitation of a fixed wavelength. Such orthogonal luminescence further facilitates intelligent applications of lanthanide materials, such as rewritable optical storage, imaging guided on-demand therapy, and the like.
In the design of orthotropic rare earth nanoparticles, different types of activator ions are typically distributed in different spatial regions of the nanoparticle by a core/multi-layer shell structure. The selective absorption and energy transfer of the sensitizers Nd 3+ and Yb 3+ to 808nm and 980nm allow excitation of different activator ions by switching the external excitation source and their luminescence is independent of each other. For example, naGdF 4:Yb/Er@NaYF4@NaYF4:Yb/Tm@NaYbF4:Nd@NaYF4 has been reported to exhibit ultraviolet and green up-conversion emissions under 808nm and 980nm laser excitation, respectively, to achieve reversible chiral inversion. Similarly, LiYbF4:Tm@LiGdF4@LiGdF4:Yb,Er@LiYF4:Nd,Yb@LiGdF4 @LiErF4:Tm@LiGdF4 is reported to emit green, blue and red light under 808nm, 980nm and 1532nm laser excitation, respectively. Clearly, most of the orthogonal up-conversion rare earth nanoparticles are limited by the complex structure of Nd 3+ and Yb 3+ co-sensitized materials, as it requires different kinds of doping ions and zoned doping. With the increase of the coating of the outer shell, the necessary long-range energy migration process inevitably causes the loss of excitation energy, resulting in the decrease of the orthogonal luminous intensity. Therefore, developing orthogonal upconverting rare earth nanoparticles with high luminescent quality and less complex structures remains a challenge.
Recent research progress shows that besides the stepped energy level structure and multiple excitation wavelengths (808 nm, 980 nm and 1530 nm) of Er 3+, naErF 4 can also enhance luminescence through self-sensitization of high-concentration Er 3+, and meanwhile, the method is an effective means for enhancing red output and realizing near-monochromatic luminescence; the coating of the inert shell can reduce surface defects so as to enhance luminescence, and meanwhile, can inhibit concentration quenching effect brought by high concentration Er 3+, and can also play a role in isolating energy transfer between two adjacent luminescent layers in a core/multi-shell structure. These advances provide opportunities for the development of structurally simple, high luminous efficiency, orthogonal upconverting rare earth nanoparticles. The problems of complex structure and low luminous efficiency of the orthogonal up-conversion rare earth nanoparticle are solved, the application of the orthogonal up-conversion nano material in the new fields of reversible light switching, super-resolution imaging, bidirectional light activation, programmable treatment and the like can be effectively promoted, and the method has important scientific significance for improving the competitiveness of China in the biomedical research field and promoting the health and social progress of human beings.
Likewise, such orthogonal luminescence properties of the nanoparticle may also be used to detect TNT and perform imaging display. The instant field identification of the trace TNT deposited on the surface can meet the national and local safety requirements of public places such as parcel sorting centers, passenger transport centers and the like. Current methods for detecting TNT residues on solid surfaces (e.g. ion mobility spectrometry, gas/liquid chromatography, etc.) are typically ex situ, involve expensive instrumentation, complex vapor sampling and pre-concentration procedures, and are not suitable for field identification of most TNTs. Therefore, developing a sensitive detection technique that is portable, visual, and easy to operate remains a challenge. Constructing a functional orthogonal luminescence sensing platform as a specific recognition element for TNT and using ratiometric fluorescence as visual signal output holds promise to address this challenge. The detection concept can be extended to the visual detection of organic molecules and biological molecules in a larger range, and has a very high practical application prospect.
Disclosure of Invention
The invention aims to solve the problems of complex structure of orthogonal up-conversion rare earth nano particles and difficult TNT in-situ detection, and to this end, a novel orthogonal up-conversion nano material with a simple structure is constructed and manufactured into portable test paper for TNT in-situ detection.
The invention firstly prepares a novel excitation orthogonal rare earth up-conversion nano probe NaErF 4@NaLuF4@NaYF4:20％Yb, 2％Er@NaLuF4 (OUCNPs) for trinitrotoluene (TNT) instant visual detection with simple structure, and realizes Nd-free 3+ doping by using self-sensitization of high-concentration Er 3+, thereby reducing the number of coating shell layers and the variety of doping ions and simplifying the structure of OUCNPs; the introduction of the inner inert shell NaLuF 4 blocks the energy transfer between the core and the light-emitting layer, realizes orthogonal light emission, has no energy migration process of long-range modulation, and can effectively reduce energy loss because excitation energy is limited to a light-emitting functional area; the coating of the outermost inert shell effectively avoids surface defects and weakening of luminescence caused by high-frequency vibration of the organic ligand, and further enhances the luminescence. Based on quenching effect of a complex formed by combining OUCNPs modified by Polyethylenimine (PEI) and TNT on OUCNPs green light under 980nm laser excitation, quantitative detection of TNT in a solution is realized according to the linear relation between the change of fluorescence intensity and TNT concentration. The TNT detection test paper is prepared, so that in-situ instant detection of TNT can be realized, imaging can be performed simultaneously, and the on-site primary screening is facilitated. The test paper is suitable for TNT field identification under most conditions, and has higher practical application value.
The invention relates to a preparation method of a luminescent center sub-structure zoned doped excitation orthogonal rare earth up-conversion nano probe, which comprises the following steps:
1. Synthesis of NaErF 4@NaLuF4@NaYF4:20％Yb,2％Er@NaLuF4 quadrature up-conversion rare earth nanoparticles of core/multishell structure: carrying out a chloride solvothermal method to prepare NaErF 4 bare cores with the particle size of 32nm, then carrying out epitaxial growth of NaLuF 4、NaYF4:20% Yb,2% Er and NaLuF 4 layer by layer on the bare cores by using an Oswald ripening method to obtain NaErF 4@NaLuF4@NaYF4:20％Yb,2％Er@NaLuF4 orthogonal up-conversion rare earth nanoparticles (OUCNPs) with the particle size of 56nm, and finally dispersing the rare earth nanoparticles into cyclohexane solution; the unit of the percentage in the above components is the molar amount;
2. Preparation of OUCNPs@PEI fluorescent probe: removing oleic acid molecular ligand on the surface of OUCNPs mmol by hydrochloric acid protonation method, adding 0.15-0.20 g PEI, stirring for 20-30 hours, coating a layer of PEI with thickness of 1.5-3.0 nm on the surface of OUCNPs by electrostatic adsorption to form hydrophilic OUCNPs@PEI fluorescent probe solution;
3. TNT detection in solution: mixing OUCNPs@PEI fluorescent probe solution with TNT acetonitrile solutions with different concentrations, wherein the concentration of OUCNPs@PEI in a final detection system is 0.52 mu mol/mL, the concentration range of TNT is 0-4000 mu M, and measuring the up-conversion luminescence emission spectrum of each mixed solution under 980nm laser excitation; it can be found that with the increase of TNT concentration, the green light integral intensity of 500-575 nm wave band is gradually weakened, and a relation curve of the green light integral intensity and TNT concentration is drawn; then mixing the OUCNPs@PEI fluorescent probe solution with TNT acetonitrile solution with unknown concentration, measuring up-conversion luminescence emission spectrum of the mixed solution under 980nm laser excitation, substituting green light integral intensity of 500-575 nm wave band into the relation curve, and calculating to obtain TNT concentration, thereby realizing quantitative detection of TNT; further, the linear detection range of TNT is 5-60 mu M, and the detection lower limit can reach 3.04 mu M;
4. In-situ instant TNT detection: preparing TNT detection test paper by immersing paper strips (any paper strip can be used, for different paper strips, the rough surface is basically presented, the prepared test paper emits light more) in OUCNPs@PEI fluorescent probe solution, and then scraping the solid surface with TNT by using the prepared test paper strip; finally, under 980nm laser excitation, the color of the test strip shows the transition from green to yellow to red along with the increase of TNT concentration, thereby realizing TNT in-situ instant detection.
The principle of the invention is as follows: the invention uses the simplified core/multi-shell structure and the realization of orthogonal luminescence as the cut-in point, and uses the self-sensitization of high-concentration Er 3+ to achieve the aim of no Nd 3+ doping, thereby simplifying the material structure; the introduction of the inner inert shell NaLuF 4 blocks the energy transfer between the core and the luminescent layer, so as to realize the aim of orthogonal luminescence. The complex formed by combining OUCNPs modified by PEI and TNT can quench green light under 980nm laser excitation, and the quantitative detection of TNT in the solution is realized according to the linear relation between the change of fluorescence intensity and TNT concentration. The TNT test paper is prepared into test paper, so that in-situ instant detection of TNT can be realized, imaging display can be carried out at the same time, and on-site screening is facilitated.
The novel orthogonal up-conversion nano probe and TNT detection with simple structure have the following advantages:
(1) Excitation of 808nm is realized without Nd 3+ doping, multiple layers of complex doping modes are avoided, and synthesis is simplified.
(2) The energy migration process without long-distance modulation avoids energy loss caused by long-distance migration and reverse energy transfer, thereby restricting the excitation light energy to the maximum extent and reducing the energy loss.
(3) Two different luminescence processes (NaErF 4 and NaYF 4:20% yb,2% er) are integrated in the same nanoparticle and separated in different substructures by an inert shell NaLuF 4, achieving their respective functions without interfering with each other: the high-concentration Er 3+ doping of 100% in NaErF 4 cores shows near-monochromatic red emission under 808nm laser excitation; under 980nm laser excitation, a dark green emission was shown.
(4) The coating of the outermost inert shell passivates the surface of the nanoparticle, effectively avoids the influence of surface ligands and solvents on luminescence, and further enhances the luminescence.
(5) OUCNPs@PEI is used as a self-reference fluorescent probe, so that the specificity recognition of TNT can be realized, colorimetric fluorescence is used as visual signal output to express the existence of TNT, and the detection lower limit can reach 3.04 mu M.
(6) The manufactured TNT detection test paper has the advantages of portability, visualization, sensitive detection, easy operation and the like, is suitable for on-site recognition of most TNT, and can be used for imaging display.
(7) The novel orthogonal up-conversion nano platform with simple structure has very wide application prospect. Meanwhile, the ratio fluorescence detection concept can be expanded to the visual detection of organic molecules and biological molecules in a larger range, and has a very high practical application prospect.
Drawings
Fig. 1: transmission electron microscopy images of OUCNPs prepared in example 1 of the present invention.
Fig. 2: OUCNPs prepared in example 1 of the present invention has emission spectra under 808nm and 980nm laser excitation, respectively.
Fig. 3: the OUCNPs@PEI fluorescent probe in detection example 1 up-converts a change curve of luminescence emission spectrum along with TNT concentration under 980nm laser excitation, wherein the luminescence intensity is normalized at 652 nm.
Fig. 4: the OUCNPs@PEI fluorescent probe in detection example 1 up-converts a relation curve of green light integral intensity and TNT concentration of 500-575 nm wave bands in a luminescence emission spectrum under 980nm laser excitation; the inset shows that the integral intensity of green light in the 500-575 nm wave band has good linear relation with TNT concentration within the range of 5-60 mu M;
fig. 5: in detection example 2, the preparation and application processes of TNT detection test paper are schematically shown.
Detailed Description
Example 1: naErF 4@NaLuF4@NaYF4:20％Yb,2％Er@NaLuF4 Synthesis of orthogonal up-conversion rare earth nanoparticles
We have properly tuned the reported chloride solvothermal method (Li, z., zhang, y., nanotechnology,2008.19, 345606) to synthesize uniformly sized, well monodisperse β -phase (hexagonal phase) NaErF 4 bare core nanoparticles. And (3) coating the shell layer by using an Oswald ripening method to form the core/multishell structure orthogonal up-conversion rare earth nanoparticle. Since in colloidal systems the energy of small particles with a larger surface to volume ratio is less stable, particles are deposited on the surface of large particles after dissolution at a height Wen Shixiao, a process called maturation. That is, under the high temperature condition, the shell precursor with small particle size can be quickly dissolved and deposited on the surface of the core nano particle with large particle size, and finally the core-shell nano particle with controllable shell thickness and uniform size is prepared.
(1) Preparation of NaErF 4 nm cores
First, erCl 3·6H2 O (1.00 mmol), 15mL Octadecene (ODE), and 6mL Oleic Acid (OA) were mixed in a 50mL flask and stirred for 30 minutes. The solution was warmed to 160℃for 30 minutes and then cooled to below 50 ℃. 8mL of a methanol solution containing NaOH (2.50 mmol) and NH 4 F (4.00 mmol) was added and heated to 75deg.C for 30min to evaporate the methanol. Then the mixture is heated to 300 ℃ for reaction for 90min, cooled to 50 ℃ after the reaction is finished, washed and centrifuged by acetone and absolute ethyl alcohol, and centrifuged for 6min (6000 r/min). Finally, the NaErF 4 bare cores obtained were dispersed in 8mL of cyclohexane for use. The whole experiment process is carried out under the protection of nitrogen and stirring.
(2) Preparation of NaLuF 4 inert Shell precursor
0.544g CF3COONa·3H2O(4mmol)、2.272g(CF3COO)3Lu·3H2O(4mmol)、 12mL Oleic acid, 12mL of oleylamine and 20mL of octadecene were poured into a 100mL three-necked flask, stirred at 120 ℃ for 30min to remove water, and then the reaction system was heated to 290 ℃ to react for 45 min. After the completion of the reaction, the reaction mixture was cooled to room temperature, and the mixture was centrifuged (6 min,6000 r/min) by washing with absolute ethanol. Finally, the resulting product was dispersed in 10mL of octadecene for use.
(3) Preparation of NaYF 4:20% Yb,2% Er Shell precursor
0.272g CF3COONa·3H2O(2mmol)、0.752g(CF3COO)3Y·3H2O(1.56 mmol)、0.226g(CF3COO)3Yb·3H2O(0.4mmol)、0.022g(CF3COO)3Er·3H2O (0.04mmol)、6mL Oleic acid, 6mL of oleylamine and 10mL of octadecene were poured into a 50mL three-necked flask, stirred at 120℃for 30min to remove water, then heated to 290℃and reacted for 45 min. After the completion of the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was centrifuged (6 min,6000 r/min) by washing with absolute ethanol. Finally, the resulting product was dispersed in 8mL of octadecene for use.
(4) OUCNPs preparation
First, a cyclohexane solution (2.0 mL) containing 0.25mmol NaErF 4 bare core nanoparticles was added to a 50mL three-necked flask containing 15mL of octadecene and 6mL of oleic acid. Then, the mixture was heated to 90℃under argon protection and kept for 30 minutes to remove the cyclohexane solvent. The mixture was then heated to 305℃at a rate of 20℃per minute. At this time, 0.75mmol of the NaLuF 4 shell precursor was injected into the three-necked flask, and the two injections were equally divided at 30 minute intervals; after 40 minutes, 1mmol of NaYF 4:20% Yb,2% Er shell precursor was split equally into two injections with a time interval of 30 minutes; after 40min of reaction, 1.5mmol of the NaLuF 4 shell precursor was again injected three times on average into a three-necked flask with a time interval of 30min, after the last injection, reacted for 1h. The system was then cooled to room temperature, centrifuged once with acetone and absolute ethanol for 6 minutes at 6000 rpm. Finally, the NaErF 4@NaLuF4@NaYF4:20％Yb,2％Er@NaLuF4 nanoparticles (OUCNPs) obtained were dispersed in 4 mL cyclohexane for use. OUCNPs A transmission electron micrograph is shown in FIG. 1, which has an average size of 56: 56 nm. FIG. 2 is a graph of the orthogonal emission spectra of OUCNPs under 808nm and 980nm excitation, respectively: emitting red light under 808nm excitation; the 980nm excitation emits green light (the human eye is more sensitive to green light, although it has a red component, and stronger green light is observed).
Example 2: OUCNPs surface modification
The detection requires transfer of the oil phase material into the aqueous phase by OUCNPs of example 1, the surface ligand being a hydrophobic Oleic Acid (OA) ligand. Here we slightly adjust the hydrochloric acid protonation method reported in the literature (Bogdan, N., vetrone, F., ozin, G.A., capobianco, J.A., nano Letters,2011,11,835-840.) by a two-step method, i.e., removing oleic acid ligand to obtain ligand-free OUCNPs, and then surface-modifying with the desired functional groups to prepare PEI-modified OUCNPs@PEI with amino ligand on the surface. The obtained nano particles not only have good dispersibility in aqueous phase solvents, but also can be combined with TNT to lay a foundation for the subsequent detection of TNT. The specific process is as follows:
(1) The 2mL OUCNPs cyclohexane solution prepared in example 1 was added to 4mL of HCl (ph=4) solution together with 2mL of cyclohexane. After vigorously stirring for 12 hours, OUCNPs originally dispersed in the cyclohexane at the upper layer is transferred to the hydrochloric acid aqueous solution at the lower layer; pumping the lower hydrochloric acid aqueous solution into a centrifuge tube, adding acetone for precipitation and centrifugation, and centrifuging for 20min and 10000r/min. The resulting centrifuged product was dispersed in 4mL of water to give an aqueous solution of OUCNPs@free without ligand.
(2) 170Mg PEI is added into the ligand-free OUCNPs aqueous solution and stirred gently for 24 hours at room temperature; centrifuging for 10min at 10000r/min, coating a layer of PEI with the thickness of 2.0nm on the surface of OUCNPs through electrostatic adsorption to form a fluorescent probe (OUCNPs@PEI), and re-dispersing the fluorescent probe in 4mL of acetonitrile after centrifuging for two times to obtain an OUCNPs@PEI acetonitrile solution, wherein the concentration of the OUCNPs@PEI fluorescent probe is 31.3 mu mol/mL.
Detection example 1, quantitative detection of TNT by OUCNPs@PEI
50. Mu.L of the OUCNPs@PEI acetonitrile solution prepared in example 3 and TNT acetonitrile solutions of different concentrations were mixed to obtain 3mL of a mixed solution of TNT of different concentrations (the final concentrations of TNT in the mixed solution were 0 μM、5μM、10μM、15μM、20μM、25μM、30μM、40μM、50μM、60μM、 70μM、80μM、90μM、100μM、200μM,400μM、500μM,1000μM、2000 μM、3000μM and 4000. Mu.M, respectively). The up-conversion luminescence emission spectra of each mixture under 980nm laser excitation were then measured. The result is shown in FIG. 3, in which the green light intensity gradually decreases as the TNT concentration increases. Meanwhile, as shown in fig. 4, the TNT concentration and the green light integral intensity of the 500-575 nm wave band have a better linear relation between 5-60 mu M, and the linear equation of I= 14.0595-0.0604C (mu M) is satisfied (wherein I is the green light integral intensity of the 500-575 nm wave band, C is the TNT concentration, and the unit is mu M).
Detection example 2 preparation of test paper from OUCNPs@PEI for detecting TNT powder
As shown in FIG. 5, we immersed cut filter papers (1 cm. Times.2 cm) in an aqueous solution of OUCNPs@PEI for about 10 minutes, adsorbed the OUCNPs@PEI onto the filter papers, and then removed and left to air dry in the dark. The above operation was repeated to obtain a batch of the same TNT test strips. On the surface of the solid (letter or cloth, this example uses letter paper), 5 drops of TNT acetonitrile solutions of different concentrations (0. Mu.M, 5. Mu.M, 15. Mu.M, 20. Mu.M, 25. Mu.M, 30. Mu.M, 50. Mu.M, 60. Mu.M, 70. Mu.M, 80. Mu.M, 90. Mu.M, 100. Mu.M, 200. Mu.M, 400. Mu.M, 1000. Mu.M, 2000. Mu.M, 3000. Mu.M and 4000. Mu.M) were each dropped to form a similar-sized patch, which was then scraped with the test paper prepared previously. The sample is irradiated by 980nm laser, and the color of the test paper is changed from green to yellow to red along with the increase of TNT concentration, so that the purpose of detecting TNT is realized. Under the excitation of 808nm laser, the test papers are red to emit light, and no obvious difference exists in visual observation, so that the test papers can be used for imaging display. In practical application, the color change is very obvious due to the uneven distribution of TNT powder, which leads to high concentration in partial areas. The TNT detection test paper has the advantages of portability, visualization, sensitive detection, easy operation and the like, is suitable for field recognition of most TNT, can perform imaging display at the same time, and has higher practical application value. The colorimetric method using a test strip can only determine a rough range, similar to the PH test strip.
Claims (8)
1. A preparation method of an excited orthogonal rare earth up-conversion nano probe for trinitrotoluene real-time visual detection comprises the following steps:
1) Synthesis of NaErF 4@NaLuF4@NaYF4: 20%Yb, 2%Er@NaLuF4 quadrature up-conversion rare earth nanoparticles of core/multishell structure: a NaErF 4 bare core with the particle size of 32 nm is prepared by a chloride solvothermal method, then NaLuF 4、NaYF4, 20% Yb, 2% Er and NaLuF 4 are epitaxially grown on the bare core layer by an Oswald ripening method, naErF 4@NaLuF4@NaYF4: 20%Yb, 2%Er@NaLuF4 orthogonal up-conversion rare earth nano particles with the particle size of 56 nm are obtained and recorded as OUCNPs, and finally OUCNPs is dispersed into cyclohexane solution; the unit of the percentage in the above components is the molar amount;
2) Preparation of OUCNPs@PEI fluorescent probe: removing oleic acid molecular ligand on the surface of OUCNPs of 0.125 mmol by a hydrochloric acid protonation method, adding 0.15-0.20 g of PEI, stirring for 20-30 hours, and coating a layer of PEI with the thickness of 1.5-3.0 nm on the surface of OUCNPs by electrostatic adsorption to form a hydrophilic OUCNPs@PEI fluorescent probe solution.
2. An excited orthogonal rare earth up-conversion nano probe for trinitrotoluene real-time visual detection is characterized in that: is prepared by the method of claim 1.
3. The use of an excited orthogonal rare earth up-conversion nanoprobe for the immediate visual detection of trinitrotoluene as claimed in claim 1 for detecting trinitrotoluene.
4. The use of an excited orthogonal rare earth upconversion nanoprobe for use in immediate visual detection of trinitrotoluene according to claim 3, wherein the use of the nanoprobe for detecting trinitrotoluene is characterized in that: TNT was detected in solution.
5. The use of an excited orthogonal rare earth up-conversion nanoprobe for the immediate visual detection of trinitrotoluene according to claim 4, wherein the use of the nanoprobe for the detection of trinitrotoluene is characterized in that: mixing OUCNPs@PEI fluorescent probe solution with TNT acetonitrile solutions with different concentrations, wherein the concentration of OUCNPs@PEI in a final detection system is 0.52 mu mol/mL, the concentration range of TNT is 0-4000 mu M, and measuring the up-conversion luminescence emission spectrum of each mixed solution under 980nm laser excitation; gradually weakening green light intensity of 500-575 nm wave bands along with the increase of TNT concentration, and drawing a relation curve of green light integral intensity of 500-575 nm wave bands and TNT concentration; and mixing the OUCNPs@PEI fluorescent probe solution with TNT acetonitrile solution with unknown concentration, measuring up-conversion luminescence emission spectrum of the mixed solution under 980nm laser excitation, substituting green light integral intensity of 500-575 nm wave band into the relation curve, and calculating to obtain TNT concentration, thereby realizing detection of TNT.
6. The use of an excited orthogonal rare earth up-conversion nanoprobe for the immediate visual detection of trinitrotoluene according to claim 5, wherein the use of the nanoprobe for the detection of trinitrotoluene is characterized in that: the TNT concentration and the green light integral intensity of the 500-575 nm wave band have a good linear relation between 5-60 mu M, and the linear equation of I= 14.0595-0.0604C is satisfied, wherein I is the green light integral intensity of the 500-575 nm wave band, C is the TNT concentration, and the unit is mu M.
7. The use of an excited orthogonal rare earth upconversion nanoprobe for use in immediate visual detection of trinitrotoluene according to claim 3, wherein the use of the nanoprobe for detecting trinitrotoluene is characterized in that: is in-situ instant TNT detection on the solid surface.
8. The use of an excited orthogonal rare earth upconversion nanoprobe for immediate visual detection of trinitrotoluene according to claim 7, wherein the use of the nanoprobe for detecting trinitrotoluene is characterized in that: preparing TNT detection test paper by immersing the paper strip in OUCNPs@PEI fluorescent probe solution, and scraping the solid surface with TNT by using the prepared TNT detection test paper; finally, under 980 nm laser excitation, the color of the TNT detection test paper shows the transition from green to yellow to red along with the increase of TNT concentration, thereby realizing TNT in-situ instant detection.
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