CN115353873A - Preparation method of fluorescent probe for regulating up-conversion luminescence based on quantum dots - Google Patents
Preparation method of fluorescent probe for regulating up-conversion luminescence based on quantum dots Download PDFInfo
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Abstract
A preparation method of a fluorescent probe for regulating up-conversion luminescence based on quantum dots comprises the following steps: preparing rare earth doped up-conversion core-shell nano materials UCNPs by adopting a high-temperature coprecipitation method; by hot injection with CsPbX 3 Preparing inorganic perovskite quantum dots QDs as a structural material, wherein X is one of Cl, br and I elements or two elements of Cl, br and I; coating water-soluble mesoporous silicon dioxide with UCNPs, and then coating the UCNPs in the mesopores of the silicon dioxideThe composite material UCNPs @ SiO is obtained by medium intervention and surface adsorption of QDs 2 + QDs; the surface of the composite material is aminated and then is connected with a molecular beacon MB to obtain a fluorescent probe MB-UCNPs @ SiO 2 + QDs. The invention can realize the regulation and control of the light-emitting position in the visible light wave band range, and the obtained fluorescent probe can realize the near infrared light excitation and the visible light wave band emission, and has high sensitivity and good specificity.
Description
Technical Field
The invention belongs to the technical field of preparation of biological nano materials, and particularly relates to a preparation method of a fluorescent probe based on quantum dot regulation and control of up-conversion luminescence.
Background
At present, excitation light sources of common fluorescent probe materials such as organic dyes, fluorescent proteins, quantum dots and the like are ultraviolet or visible light generally, fluorescence emission peaks are wide and asymmetric, tailing is serious, spectra of various dyes are overlapped, very strong biological autofluorescence (background fluorescence) and scattered light exist, and application of the fluorescent probe materials is limited seriously. In contrast, the upconversion nanoparticles (UCNPs for short) use near-infrared light as excitation light, which causes less light damage, and the biological tissue has a lower autofluorescence background, a stronger penetration depth, multi-wavelength luminescence, almost no toxicity, high fluorescence intensity and high stability, so the UCNPs are used as a novel fluorescent probe material, and the unique advantages of the upconversion nanoparticles can effectively and significantly overcome the defects of the conventional fluorescent probe, and are widely applied in the fields of cancer diagnosis and treatment, fluorescence imaging, biological detection and the like. However, the discrete energy levels of the rare earth ions lead to the fixation of the emission band of the fluorescent probe, so that the regulation cannot be realized, and the optimal absorption characteristic of the detected target object is difficult to match.
In order to realize tunability of an upconversion nanomaterial as a fluorescent probe and solve the defects of a common fluorescent probe material, a novel method for combining upconversion with other receptor materials is designed in the prior art to prepare a composite material, for example, cadmium telluride quantum dot, gold nanoparticles, graphene and the like form fluorescence resonance energy transfer with upconversion, so that the limitation of respective application of the upconversion and the receptor materials is broken, near-infrared excitation is realized, and emitted light in a visible light waveband range is obtained. The multi-emission peak position of the obtained composite material is utilized to realize a multi-color anti-counterfeiting and multi-color imaging system, and the results can be contrasted and analyzed through different colors, however, the energy transfer process between up-conversion and receptors is not fully utilized, the optimal detection peak position required by a target object cannot be obtained, the precise specific identification of the detected target object cannot be achieved, and the application in the aspect of biological detection is severely limited.
Disclosure of Invention
The invention aims to provide a preparation method of a fluorescent probe for regulating up-conversion luminescence based on quantum dots, which can realize regulation and control of luminescence positions in a visible light waveband range by regulating the proportion of halogen elements doped in the quantum dots in a composite material; the prepared fluorescent probe can realize near infrared light excitation and visible light wave band emission, has small biological damage, stronger penetrating power, high sensitivity and good specificity, and provides favorable basis for early discovery and diagnosis and treatment of diseases.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of a fluorescent probe for regulating and controlling up-conversion luminescence based on quantum dots comprises the following steps:
(1) Adopting high-temperature coprecipitation method to prepare NaYF 4 As a substrate material, yb is selected as a sensitizer, and Tm is selected as a luminescent ion to prepare rare earth doped up-conversion core-shell nano materials UCNPs; by hot injection with CsPbX 3 The CsPbX is used as a structural material to prepare inorganic perovskite quantum dots QDs 3 In the formula, X is one of Cl, br and I elements or two elements of Cl, br and I;
(2) Coating the rare earth doped up-conversion core-shell nano material UCNPs prepared in the step (1) on the mesoporous silica with water solubility, and then intervening in the mesopores of the silica and adsorbing the inorganic perovskite quantum dots QDs prepared in the step (1) on the surface to obtain the composite material UCNPs @ SiO 2 +QDs；
(3) To composite material UCNPs @ SiO 2 Amination treatment is carried out on the surface of the + QDs, and then the obtained product is connected with a molecular beacon MB to obtain a fluorescent probe MB-UCNPs @ SiO 2 +QDs。
Further, in the step (1), the structural formula of the rare earth doped up-conversion core-shell nano material UCNPs is NaY 1-x-y F 4 :Yb x ，Tm y @NaY 1-z F 4 :Yb z UCNPs are prepared from nano material NaY with up-conversion core structure 1-x-y F 4 :Yb x ，Tm y And an up-conversion shell structure nano material NaY 1-z F 4 :Yb z In the formula, x and y are respectively Yb with a core structure 3+ 、Tm 3+ The mol ratio of doping is that x is more than or equal to 0.2 and less than or equal to 0.3,0.002 and less than or equal to 0.01, and z is Yb with a shell structure 3+ The doping molar ratio is more than or equal to 0.05 and less than or equal to 0.1.
Preferably, in the step (1), the molar ratio between the upconversion core structure nanomaterial and the upconversion shell structure nanomaterial is 2:1, the grain diameter of the rare earth doped up-conversion core-shell nano material UCNPs is 30-40nm.
Preferably, in the step (1), the particle size of the inorganic perovskite quantum dots QDs is 10 to 20nm.
Further, in the step (2), a structure directing agent CTAB is used as a template and TEOS is used as a raw material, and the water-soluble mesoporous silica is obtained under the condition that the pH value is 8-9; the volume-mass ratio of the TEOS dose to the CTAB weight is 1.5-2 ml/g.
Preferably, in the step (2), the mesoporous size of the silicon dioxide is 2-4nm, the thickness of a coating layer of the rare earth doped up-conversion core-shell nano material UCNPs is 50-80nm, and the composite material UCNPs @ SiO 2 The size of + QDs is 80-110nm.
In order to achieve better light intensity, it is preferable that, in step (2), UCNPs @ SiO 2 Mass ratio to QDs 20:0.3.
further, in the step (3), a silane agent APTES is used for treating the composite material UCNPs @ SiO 2 Amination treatment is carried out on the surface of the QDs, and the dosage of the silane agent APTES is 0.25-0.5 ml/gUCNPs @ SiO 2 +QDs。
Further, in the step (3), two ends of the molecular beacon are respectively connected with a carboxylation group and a BHQ1 quenching group, and the molecular beacon is prepared by reacting the two molecular beacons in a molar ratio of 1:1 NHS/EDC, and the molecular beacon is connected to the composite material UCNPs @ SiO through amide reaction of carboxyl group 2 + QDs.
Preferably, in step (3), in order to ensure that the fluorescence intensity of the fluorescent probe is weak and reduce the interference of background signals to the maximum extent, so that the detection effect of the obtained fluorescent probe is better, the composite material of the molecular beacon MB after amination treatment is usedMaterial UCNPs @ SiO 2 The concentration of the + QDs solution is 0.8-1 μ M.
The invention combines the up-conversion material and the perovskite quantum dots, makes up the defect that the visible light wave band can not be tunable due to discrete energy levels of rare earth ions through the perovskite quantum dots, and breaks through the limitation of the two on the application aspect of biological fluorescence detection by utilizing the Fluorescence Resonance Energy Transfer (FRET) principle. In addition, the invention realizes the regulation and control of the light-emitting position in the visible light wave band range by regulating the proportion of the halogen element doped in the quantum dots in the composite material. Selecting a composite material obtained by combining a rare earth doped up-conversion core-shell nano material with perovskite quantum dots (Br: I = 0.7. The fluorescent probe prepared by the invention can realize near infrared light excitation and visible light wave band emission, has small biological damage, stronger penetrating power, high sensitivity and good specificity, can carry out low-concentration detection and specificity identification on miRNA of various diseases (cancer, tumor and cardiovascular disease), and is beneficial to realizing early discovery and diagnosis of the diseases.
Compared with the prior art, the invention has the following advantages:
(1) Near infrared excitation, emission in the visible band: the invention uses the composite material of rare earth up-conversion core-shell nano material and perovskite quantum dots to realize near infrared light excitation and emission in a visible light wave band, thereby reducing the damage to biological tissues and having better penetration effect;
(2) The biocompatibility is high: according to the invention, the mesoporous silicon dioxide and the silane agent are used for coating and modifying the composite material, so that the biocompatibility and the hydrophilicity of the up-conversion nano material are greatly increased, and the detection of biological application can be realized;
(3) The emission peak has wide regulation range: according to the invention, the different proportions and sizes of the QDs doped halogen elements (X = Cl, br, I) in the composite material are adjusted, so that accurate regulation and control luminescence covering the visible light in a full-wave range is realized;
(4) Optionally: the invention can adjust UCNPs @ SiO according to the absorption characteristic of the detected target object 2 And the optimal emission peak position of the + QDs completes the optimal detection effect on the target object.
Drawings
FIG. 1 shows the upconversion UCNPs (a), perovskite quantum dots QDs (b) and mesoporous silica-coated upconversion UCNPs @ SiO prepared in this example 2 (c) Composite material UCNPs @ SiO 2 TEM image of + QDs (d);
FIG. 2 is the mesoporous silica coated up-conversion UCNPs @ SiO prepared in this example 2 And composite materials UCNPs @ SiO 2 N of + QDs 2 Isothermal adsorption and desorption curve diagram;
FIG. 3 shows the composite material UCNPs @ SiO 2 + QDs are doped with halogen elements in different proportions respectively and have fluorescence spectrograms under excitation of 980nm excitation light;
FIG. 4 shows UCNPs @ SiO 2 A fluorescence spectrum under excitation with 980nm excitation light and an absorption spectrum of QDs (Br: I = 0.7;
FIG. 5 is UCNPs @ SiO 2 A fluorescence spectrum of + QDs (Br: I = 0.7) under excitation with 980nm excitation light and an absorption spectrum of molecular beacon MB-BHQ 1;
FIG. 6 shows MB-UCNPs @ SiO 2 Fluorescence spectrum of + QDs fluorescent probe under excitation of 980nm excitation light.
Detailed Description
The invention is described in further detail below with reference to the figures and the specific embodiments.
A preparation method of a fluorescent probe for regulating up-conversion luminescence based on quantum dots comprises the following steps:
(1) Adopting high-temperature coprecipitation method to prepare NaYF 4 The method is characterized in that Yb is selected as a sensitizer and Tm is selected as a luminescent ion to prepare the rare earth doped up-conversion core-shell nano material UCNPs, and the specific preparation method comprises the following steps:
(1-1) to prepare 2mmol NaY 0.795 F 4 :Yb 0.2 ，Tm 0.005 The nano material is taken as an example: according to the formula NaY 0.795 F 4 :Yb 0.2 ，Tm 0.005 Molar ratio of the elements in (1.39) mmol YCl 3 ·6H 2 O、0.6mmol YbCl 3 ·6H 2 O and 0.01mmol of TmCl 3 ·6H 2 O in a three-neck round-bottom flask, 12mL of oleic acid and 30mL of octadecene are added, the bottle mouth is plugged, and 10minN is firstly introduced 2 The flask was vented and then purged with N 2 Heating to 120 ℃ under protection and magnetic stirring for reaction for 10min, exhausting oxygen in the flask, heating to 160 ℃, continuously heating and stirring for 60min to obtain a dissolved rare earth chloride light yellow solution, and naturally cooling to 50 ℃ for later use;
(1-2) slowly dropwise adding 10mL of methanol solution in which 8.0mmol of ammonium fluoride and 5.0mmol of sodium hydroxide are dissolved into the light yellow solution of the rare earth chloride, continuously stirring at 50 ℃ for reacting for 40min to enable the ammonium fluoride and the 5.0mmol of sodium hydroxide to be completely dissolved in the mixed solution, heating to 80 ℃ to volatilize the methanol, continuously bubbling the mixed solution when the methanol is volatilized, continuously heating the mixture to 120 ℃ and preserving the temperature for 10min until no bubble is generated in the solution, finally heating to 300 ℃ to react for 90min, and naturally cooling to room temperature;
(1-3) after the mixed liquid in the step (1-2) is cooled to room temperature, dispersing the mixed liquid in cyclohexane, centrifuging the mixed liquid for 5min at the rotating speed of 8000rpm/min to obtain a precipitate, repeating the steps with the cyclohexane, centrifuging and washing for three times, and finally obtaining the nano-particle NaY with the up-conversion nuclear structure 0.795 F 4 :Yb 0.2 ，Tm 0.005 Dispersing in cyclohexane for storage;
(1-4) to prepare 1mmol of NaY 0.9 F 4 :Yb 0.1 The up-conversion shell structure nano material is taken as an example: weigh 0.9mmolYCl 3 ·6H 2 O、0.1mmolYbCl 3 ·6H 2 Adding 6mL of oleic acid and 15mL of octadecene into O chloride in a three-neck round-bottom flask, heating to 160 ℃ to obtain a light yellow transparent mixed solution, and cooling to room temperature;
(1-5) preparation of NaY 0.795 F 4 :Yb 0.2 Tm 0.005 @NaY 0.9 F 4 :Yb 0.1 Rare earth doped up-conversion core-shell nano-material UCNPs: will step withSynthesis of Up-converting Nuclear Structure nanoparticles NaY for subsequent use in step (1-3) 0.795 F 4 :Yb 0.2 ，Tm 0.005 Adding the solution into the NaY prepared in the step (1-4) 0.9 F 4 :Yb 0.1 Heating the chloride solution of the up-conversion shell structure nano material to 80 ℃, keeping the temperature for 30min to remove cyclohexane in the mixed solution, then naturally cooling to 50 ℃, slowly adding 5mL of methanol solution in which 4.0mmol of ammonium fluoride and 2.5mmol of sodium hydroxide are dissolved into the mixed solution, and continuously stirring and reacting for 30min at 50 ℃ to fully dissolve the mixture; heating to 80 ℃ to evaporate the methanol, continuously bubbling the solution during the methanol volatilization, continuously heating the mixture to 120 ℃ and preserving the temperature for 10min until no bubbles are generated in the solution; finally heating the mixture to 300 ℃ for reaction for 90min, and naturally cooling the mixture to room temperature after the reaction is finished;
(1-6) dispersing the mixed solution obtained in the step (1-5) in cyclohexane, centrifuging the mixed solution for 5min at the rotating speed of 8000rpm/min to obtain a precipitate, re-centrifuging and washing the precipitate for three times by using cyclohexane, and finally obtaining the up-conversion core-shell nano material NaY 0.795 F 4 :Yb 0.2 ，Tm 0.005 @NaY 0.9 F 4 :Yb 0.1 Dispersed in cyclohexane as upconversion UCNPs nanoparticles, and its TEM image is shown in fig. 1 (a). As can be seen from fig. 1 (a), the material is in the hexagonal phase with an average particle size of 32nm. By hot injection with CsPbX 3 The CsPbX is used as a structural material for preparing inorganic perovskite quantum dots QDs 3 In the formula, X is one of Cl, br and I elements or two elements of Cl, br and I; the preparation method comprises the following steps:
preparing a Cs precursor: 0.203g of CS 2 CO 3 1ml of oleic acid OA, 10ml of 1-octadecene ODE were poured into a 100ml three-neck round-bottom flask, and N was introduced for 10min 2 Exhausting air in the flask, heating to 120 ℃, keeping the temperature for 10min, exhausting oxygen in the flask, heating to 150 ℃, stirring for about 60min, and naturally cooling to room temperature to obtain cesium oleate; since cesium oleate precipitates from ODE in the form of a precipitate at normal temperature, it must be preheated to 100 ℃ before use;
QDs(X＝Cl，Br，i) Preparing quantum dots: weigh 0.188mmol of PbX 2 (Cl, br, I) in a 50ml three-necked flask, 5ml of 1-octadecene ODE was added, and N was introduced for 10min 2 The air in the flask was vented and the temperature was raised to 120 deg.C (if PbCl was used) 2 When the dissolution temperature is raised to 150 ℃ C. For 30min, 1.5mL of oleic acid OA and 1.5mL of oleylamine Oam are added and PbX is waited 2 And (3) completely dissolving, heating to 170 ℃, preserving the temperature for 30min, then quickly injecting 0.4ml of precursor cesium oleate (heating to 100 ℃ before use), and cooling in an ice water bath after 5 s. Dispersing in n-hexane, centrifuging the mixed solution at 6000rpm/min for 5min to obtain precipitate, washing with n-hexane twice, and drying to obtain quantum dot nanocrystalline powder.
Taking QDs (Br: I = 0.7) as an example, a TEM image of the prepared perovskite quantum dots QDs is shown in fig. 1 (b), and the perovskite quantum dots QDs have a tetragonal structure and an average particle diameter of about 11nm. The absorption spectrum is shown in fig. 4, a smaller absorption peak position is arranged in front of the position corresponding to the emission peak, the absorption is stronger in the short wavelength range, and the absorption is weaker in the long wavelength range.
(2) Coating water-soluble mesoporous silica with rare earth doped up-conversion core-shell nano material UCNPs, and then intervening in the mesopores of the silica and adsorbing inorganic perovskite quantum dots QDs on the surface to obtain a composite material UCNPs @ SiO 2 + QDs, the specific preparation method is as follows:
(2-1) taking rare earth doped up-conversion core-shell nano-material UCNPs as an inner core, firstly washing oleic acid on the surface of up-conversion nano-particles by using a hydrochloric acid solution, weighing 20mg of UCNPs, dissolving the UCNPs in 2ml of cyclohexane solution, adding 4ml of hydrochloric acid solution, stirring for 2h, centrifuging for 5min at 10000r/min, washing for three times by using deionized water, and placing in 1ml of deionized water for standby;
(2-2) preparing mesoporous silica using cetyltrimethylammonium bromide (CTAB) to coat the hydrophilic UCNPs nanoparticles obtained in the step (2-1): 0.02g of hexadecyl trimethyl ammonium bromide (CTAB) is dissolved in 2mL of deionized water, stirring is carried out for 10min, the CTAB can be used for controlling the size of mesopores, UCNPs nano-particle solution obtained in the step (2-1) is added, and 2mL of ethanol and 50ul of strong ammonia water solution (28 wt.%) are adopted for adjustmentThe pH of the solution is 9, the solution is stirred for 30min, then 40ul of Tetraethoxysilane (TEOS) is slowly added into the solution, the TEOS is used for controlling the thickness of a coated layer, and after the reaction is carried out for 6h, the solution is washed by ethanol and water for 3 times; in order to obtain mesoporous SiO coated by the rare earth doped up-conversion core-shell nano material UCNPs 2 The structure, structure directing agent (CTAB) to remove surface, is washed with mixed solution of hydrochloric acid and ethanol (20 ul hydrochloric acid solution and 1ml ethanol solution) at 80 deg.C under reflux for three times, and dried in drying oven at 80 deg.C for 24 hr to obtain UCNPs @ SiO 2 And (3) powder. Prepared UCNPs @ SiO 2 TEM of (4) is shown in FIG. 1 (c), UCNPs @ SiO 2 The morphology of (A) is spherical, and the average particle size is about 97nm. The fluorescence spectrum is shown in FIG. 4, UCNPs @ SiO 2 Has strong luminous intensity at 345nm, 362nm, 450nm, 477nm, 645nm and 802nm, and UCNPs @ SiO 2 Emission peaks at 345nm, 362nm, 450nm and 477nm overlap with the strong absorption range of QDs (Br: I = 0.7.
(2-3) preparation of novel composite nanomaterial UCNPs @ SiO 2 + QDs (Br: I =0.7: is completed by solvent evaporation, and 20mg of UCNPs @ SiO prepared in step (2-2) 2 Dissolving in 2ml n-hexane, magnetically stirring at 40 deg.C, and condensing and refluxing for 30min to obtain UCNPs @ SiO 2 Can be completely dispersed, then 0.3mg of quantum dot QDs (Br: I = 0.7) solution prepared in the step (1) is added, magnetic stirring is continued for 30min, finally the solution is cooled to room temperature, and n-hexane is used for washing for three times to obtain the novel composite nano material UCNPs @ SiO 2 + QDs (Br: I = 0.7) and TEM obtained is shown in fig. 1 (d), and QDs are seen to be inserted in the mesopores and adsorbed on the surface of the mesoporous silica due to their small size. N thereof 2 The isothermal adsorption-desorption curve is shown in FIG. 2, when P/P 0 Above 0.28, the adsorption capacity begins to increase slowly and the adsorption rate remains constant, which indicates that the pore channel has good uniformity and small pore diameter. After QDs addition, the adsorption curve rate becomes slower and the gap between curves decreases. The obtained fluorescence spectrum is shown in FIG. 5, UCNPS @ SiO 2 + QDs are new at the 531nm positionCorresponds to the position of the strong absorption peak of BHQ1 on MB, thereby accomplishing the quenching effect.
(3) To composite material UCNPs @ SiO 2 Amination treatment is carried out on the surface of the + QDs, and then the obtained product is connected with a molecular beacon MB to obtain a fluorescent probe MB-UCNPs @ SiO 2 + QDs, the specific preparation process is as follows:
(3-1) preparation of aminated composite nanomaterial UCNPs @ SiO 2 + QDs: taking 20mg of UCNPs @ SiO in the step (2) 2 + QDs is dispersed in 2ml cyclohexane, under magnetic stirring, slowly dripping 10ul of APTES silane agent, stirring for 60min, realizing amination on the surface of the composite material by utilizing trace hydrolysis of APTES in cyclohexane, and washing twice by using absolute ethyl alcohol solution;
(3-2) preparation of novel fluorescent Probe MB-UCNPs @ SiO 2 + QDs: taking out 1ml of aminated nano material UCNPs @ SiO in step (3-1) 2 + QDs solution, weigh 5mgEDC and 5mgNHS to add to solution, shake shaking to make fully dissolve; adjusting pH to about 6.5 with 2 μ M hydrochloric acid solution, performing shake reaction at room temperature for 30min, and fully reacting to activate amino; appropriate amount of amino activated nano material UCNPs @ SiO 2 Mixing the + QDs solution and 1 μ M MB solution in a centrifuge tube, reacting for 30min by a shaking table, finally centrifuging and washing the reactant twice at 10000rpm/min, centrifuging for 5min, completing the whole process in an absolute ethyl alcohol solution, and storing at 4 ℃ to obtain the novel fluorescent probe MB-UCNPs @ SiO 2 + QDs. Under the excitation of 980nm exciting light, the obtained fluorescence spectrogram is shown in fig. 6, and as BHQ1 quenching groups on MB are close to the surface of the composite material, the light intensity at the 531nm position is weakened, and the fluorescence probe with weak background signals is obtained.
According to the invention, on the basis of the up-conversion core-shell nano material, a structural template agent CTAB is used as a template to prepare the up-conversion nano particles coated with mesoporous silica, and the mesoporous silica can increase the adsorption performance and has better hydrophilicity and biocompatibility. The invention synthesizes the novel composite nano material UCNPs @ SiO with more excellent luminescence property 2 + QDs, under the excitation of 980nm near infrared exciting light, the emission of the up-conversion nano material is regulated and controlled by changing the QDs combined in the composite materialThe location of the light. Simultaneously, the surface of the material is aminated to prepare a novel fluorescent probe MB-UCNPs @ SiO which is excited by near infrared light and emits in visible light wave band 2 + QDs, while ensuring the luminescent properties of the material, increases the functionality of the material.
In other embodiments, the doping ratio of halogen elements (Cl, br, I) of quantum dots in the composite material can be changed according to the position of emitted light required by a target, and the obtained fluorescence spectrogram is shown in FIG. 3, wherein the doping ratios of sample 1 to sample 9 are (1) UCNPs @ SiO 2 +QDs(Cl:Br＝0.9:0.1)；(2)UCNPs@SiO 2 +QDs(Cl:Br＝0.7:0.3)；(3)UCNPs@SiO 2 +QDs(Cl:Br＝0.5:0.5)；(4)UCNPs@SiO 2 +QDs(Cl:Br＝0.3:0.7)；(5)UCNPs@SiO 2 +QDs(CsPbBr 3 )；(6)UCNPs@SiO 2 +QDs(Br:I＝0.7:0.3)；(7)UCNPs@SiO 2 +QDs(Br:I＝0.5:0.5)；(8)UCNPs@SiO 2 +QDs(Br:I＝0.3:0.7)；(9)UCNPs@SiO 2 + QDs (Br: I = 0.1. It can be seen from the figure that, with the change of the proportion of the halogen element doped in the composite material, the obtained new emission peak is red-shifted in the visible light range of 400nm-700nm, thereby realizing the tunability. The preparation steps are basically consistent with those described above, so that the ideal luminescence peak position required by the target object can be obtained, and the modification is carried out to obtain a new fluorescent probe, thereby better completing the detection of the target object.
Claims (10)
1. A preparation method of a fluorescent probe for regulating up-conversion luminescence based on quantum dots is characterized by comprising the following steps:
(1) Adopting high-temperature coprecipitation method to prepare NaYF 4 Preparing rare earth doped up-conversion core-shell nano materials UCNPs by selecting Yb as a sensitizer and Tm as luminescent ions as substrate materials; by hot injection with CsPbX 3 The CsPbX is used as a structural material for preparing inorganic perovskite quantum dots QDs 3 In the formula, X is one of Cl, br and I elements or two elements of Cl, br and I;
(2) Coating the water-soluble mesoporous silica with the rare earth-doped up-conversion core-shell nano material UCNPs prepared in the step (1), and then coating the mesoporous silica with the water-soluble mesoporous silica in the mesopores of the silicaThe inorganic perovskite quantum dots QDs prepared in the step (1) of intervention and surface adsorption are used for obtaining the composite material UCNPs @ SiO 2 +QDs；
(3) To composite material UCNPs @ SiO 2 Amination treatment is carried out on the surface of the + QDs, and then the obtained product is connected with a molecular beacon MB to obtain a fluorescent probe MB-UCNPs @ SiO 2 +QDs。
2. The method for preparing a fluorescent probe based on quantum dot regulated up-conversion luminescence according to claim 1, wherein in the step (1), the structural formula of the rare earth doped up-conversion core-shell nano material UCNPs is NaY 1-x-y F 4 :Yb x ，Tm y @NaY 1-z F 4 :Yb z UCNPs are prepared by up-conversion nuclear structure nano material NaY 1-x-y F 4 :Yb x Tm y And the nano material NaY with the up-conversion shell structure 1-z F 4 :Yb z In the formula, x and y are respectively Yb with a core structure 3+ 、Tm 3+ The mol ratio of doping is that x is more than or equal to 0.2 and less than or equal to 0.3,0.002 and less than or equal to 0.01, and z is Yb with a shell structure 3+ The doping molar ratio is more than or equal to 0.05 and less than or equal to 0.1.
3. The method for preparing a fluorescent probe based on quantum dot regulated up-conversion luminescence of claim 2, wherein in the step (1), the molar ratio of the up-conversion core structure nanomaterial to the up-conversion shell structure nanomaterial is 2:1, the grain diameter of the rare earth doped up-conversion core-shell nano material UCNPs is 30-40nm.
4. The method for preparing a fluorescent probe based on quantum dot regulated up-conversion luminescence according to claim 1 or 2, wherein in the step (1), the particle size of the inorganic perovskite quantum dots QDs is 10-20nm.
5. The method for preparing a fluorescent probe based on quantum dot regulated up-conversion luminescence according to claim 1 or 2, wherein in the step (2), a structure directing agent CTAB is used as a template and TEOS is used as a raw material, and the obtained mesoporous silica has water solubility under the condition of pH 8-9; the volume-mass ratio of the TEOS dose to the CTAB weight is 1.5-2 ml/g.
6. The method for preparing the fluorescent probe based on quantum dot regulated up-conversion luminescence of claim 5, wherein in the step (2), the mesoporous size of the silica is 2-4nm, the thickness of the coating layer of the rare earth doped up-conversion core-shell nano material UCNPs is 50-80nm, and the composite material UCNPs @ SiO is 2 The size of + QDs is 80-110nm.
7. The method for preparing a fluorescent probe based on quantum dot regulated up-conversion luminescence according to claim 1 or 2, wherein in the step (2), UCNPs @ SiO 2 Mass ratio to QDs 20:0.3.
8. the method for preparing a fluorescent probe based on quantum dot regulated up-conversion luminescence of claim 1 or 2, wherein in the step (3), silane agent APTES is used for applying to the composite material UCNPs @ SiO 2 Amination treatment is carried out on the surface of the QDs, and the dosage of the silane agent APTES is 0.25-0.5 ml/gUCNPs @ SiO 2 +QDs。
9. The method for preparing a fluorescent probe based on quantum dot regulated up-conversion luminescence according to claim 1 or 2, wherein in the step (3), two ends of the molecular beacon are respectively connected with a carboxylation group and a BHQ1 quenching group, and the molecular beacon is prepared by performing the following steps of (1) at a pH of 6.0-6.5 in a molar ratio of: 1 NHS/EDC, and the molecular beacon is connected to the composite material UCNPs @ SiO through amide reaction of carboxyl group 2 + QDs.
10. The method for preparing the fluorescent probe based on quantum dot regulated up-conversion luminescence according to claim 1 or 2, wherein in the step (3), the molecular beacon MB is made of a composite material UCNPs @ SiO after amination treatment 2 The concentration of the + QDs solution is 0.8-1 μ M.
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| CN112484851A (en) * | 2021-01-06 | 2021-03-12 | 福州大学 | Perovskite lanthanide series composite nano material, preparation method thereof and application of perovskite lanthanide series composite nano material in broadband photoelectric detector |
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| CN108624317A (en) * | 2018-07-12 | 2018-10-09 | 京东方科技集团股份有限公司 | A kind of core-shell type quantum point and its preparation method and application |
| CN112484851A (en) * | 2021-01-06 | 2021-03-12 | 福州大学 | Perovskite lanthanide series composite nano material, preparation method thereof and application of perovskite lanthanide series composite nano material in broadband photoelectric detector |
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