CN105018070A - Preparation method of mercury ion rate probe based on rhodamine derivative and quantum dot fluorescent microsphere - Google Patents
Preparation method of mercury ion rate probe based on rhodamine derivative and quantum dot fluorescent microsphere Download PDFInfo
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- CN105018070A CN105018070A CN201410160526.6A CN201410160526A CN105018070A CN 105018070 A CN105018070 A CN 105018070A CN 201410160526 A CN201410160526 A CN 201410160526A CN 105018070 A CN105018070 A CN 105018070A
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Abstract
The invention relates to a preparation method of a mercury ion rate probe based on a rhodamine derivative and a quantum dot fluorescent microsphere. The preparation method comprises the steps of firstly, preparing a water-soluble quantum dot (CdTe:Zn) by using a water-phase synthesis method, and synthesizing a silicon dioxide nanoparticle by using a reverse-phase microemulsion method, wherein Zn<2+> is doped into the water-soluble quantum dot, the surface of the water-soluble quantum dot is provided with mercaptopropionic acid (MPA), and the quantum dot is doped into the silicon dioxide nanoparticle; then, preparing a lactamized rhodamine derivative with specific recognition capability for Hg<2+>, and modifying siloxy through aminopropyltriethoxysilane (APS) on the basis, so that the lactamized rhodamine derivative is connected with the silicon dioxide nanoparticle; and finally, grafting the rhodamine derivative onto the surface of the silicon dioxide nanoparticle to construct the mercury ion rate probe based on FRET. By using the probe, not only is the interference of the external environment to the optical property of the quantum dot reduced, but also the distance from an energy donor (the quantum dot) to an energy acceptor (the rhodamine derivative) is shortened, the energy transfer efficiency of FRET is increased, and furthermore the mercury ion detection sensitivity is enhanced.
Description
Technical field
The invention belongs to fluorescent probe and preparation field thereof, particularly a kind of preparation method of the mercury ion ratio probes based on Rhodamine Derivatives and quantum dot fluorescence microballoon.
Background technology
The application of fluorescence nano sensor in biological detection, environmental monitoring, cell imaging, drug conveying, disease diagnosis and therapy etc. has caused the extensive concern of people.The method of machine-processed structure biology, chemistry and the physical sensors for we providing a kind of novelty of FRET (fluorescence resonance energy transfer), the steric effect of its uniqueness and spectral effects impart the outstanding performance of these sensors.Such as, energy trasfer can be used for design ratio fluorescent probe.Compared with single signal fluorescent probe, ratio probes efficiently avoid the interference of concentration and probe concentration, probe environment and excitation intensity, drastically increases sensitivity and the accuracy of detection.And, for space length strict between acceptor in energy transfer system, for the conformational change kinetics and interaction mechanism exploring biomolecules (as RNA, DNA, protein) provides desirable nanometer chi.In addition, based in the sensor of energy trasfer, the acceptor (such as organic fluorescent dye) of many narrowband excitation itself is again as specific probe parts, by exciting the wide excited donor (such as quantum dot) matched with acceptor, that has indirectly expanded acceptor excites scope, facilitates the probe that design has broadband excitation and high specific concurrently.
Heavy metal ion, such as Hg
2+, with the physiological process of the mankind, the generation of various disease is closely related with environmental pollution.Be conventionally used to the method detecting heavy metal ion, comprise chemistry titration, atomic fluorescence, atomic absorption, atomic emissions and ICP-MS etc., there is many problems, such as operating process is complicated, and inadequate economic dispatch, the detection for heavy metal ion brings much inconvenience.In recent years, along with the successful synthesis of the Rhodamine Derivatives of fluorescent nano material and lactamize, the heavy metal ion in Real-Time Monitoring environment becomes possibility.These materials are also laid a good foundation for the structure based on FRET sensor, have enriched the means detecting heavy metal ion.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of the mercury ion ratio probes based on Rhodamine Derivatives and quantum dot fluorescence microballoon.Mercury ion ratio probes prepared by the method makes have the lactamize Rhodamine Derivatives of specific recognition capability to modify siloxy to mercury ion by aminopropyl triethoxysilane (APS), facilitates the connection with the multi-layer silica dioxide nanoparticle being doped with quantum dot.The external environment that this probe not only effectively reduces is to the interference of quantum dot optical property, and the distance reduced between energy donor (quantum dot) and energy acceptor (Rhodamine Derivatives), improve the energy transfer efficiency of FRET, and then enhance the susceptibility detecting mercury ion.
A kind of mercury ion probe based on Rhodamine Derivatives and quantum dot fluorescence microballoon of the present invention, is characterized in that: the structural formula of described Rhodamine Derivatives is:
The preparation method of a kind of mercury ion probe based on Rhodamine Derivatives and quantum dot fluorescence microballoon of the present invention, comprising:
(1) add in intermediate water by sodium borohydride and tellurium powder, under 4 DEG C of nitrogen protections, reaction obtains sodium hydrogen telluride in 8 hours; Wherein the mass volume ratio of sodium borohydride, tellurium powder, intermediate water is 0.285g: 0.32g: 10ml;
(2) Cadmium chloride fine powder, zinc chloride, thiohydracrylic acid are joined in intermediate water, and use sodium hydrate regulator solution PH=11, add above-mentioned tellurium sodium cyanide after deoxygenation and be transferred in reactor and put into baking oven and react; Wherein the mass volume ratio of Cadmium chloride fine powder, zinc chloride, thiohydracrylic acid, tellurium sodium cyanide, intermediate water is: 0.114g: 0.682g: 0.105ml: 0.4ml: 100ml;
(3) be dissolved in solvent by rhodamine B, add three (2-aminoethyl) amine, heated and stirred backflow at 80 DEG C, add methylene dichloride and intermediate water after rotary evaporation of solvent, washing and filtering is spin-dried for, and purifies, obtains RHB-NH2; Wherein the mass volume ratio of rhodamine B, three (2-aminoethyl) amine, methylene dichloride, intermediate water, solvent is: 1.5g: 4.8ml: 50ml: 100ml: 30ml;
(4) by RHB-NH
2be dissolved in solvent, add isocyanatopropyl triethoxyl silane and triethylamine, stirring and refluxing at 80 DEG C, purifying after rotary evaporation of solvent obtains Rhodamine Derivatives; Wherein RHB-NH
2, isocyanatopropyl triethoxyl silane, triethylamine mass volume ratio be: 0.2g: 0.2ml: 0.4ml;
(5) in the CdTe:Zn quantum dot aqueous solution, hexanaphthene, Triton X-100, n-hexyl alcohol is added, lucifuge stirs, add to continue to add after APTES and TEOS has stirred after TEOS and ammoniacal liquor continue to stir and add Rhodamine Derivatives, react the mercury ion probe terminating rear eccentric cleaning and obtain based on multilayered fluorescent Nano microsphere and Rhodamine Derivatives.Its cyclohexane, Triton X-100, n-hexyl alcohol, TEOS, ammoniacal liquor, APTES, volume ratio are: 15ml: 3.54ml: 3.6ml: 0.2ml: 0.12ml: 0.04ml.
In described step (3), solvent is anhydrous methanol.
Purify in described step (3) as silica gel column chromatography is purified, eluent is: CH
2cl
2/ MeOH/Et
3n=40: 2: 1.
In described step (4), solvent is toluene.
Purify in described step (4) as silica gel column chromatography is purified, eluent is: CH
2cl
2/ CH
3oH=5: 1.
Described step adds APTES and TEOS in (5).
Mercury ion ratio probes detection method is: diluted by a certain percentage by mercury ion ratio probes dispersion liquid HEPES buffered soln (PH=7) of preparation, using HEPES buffered soln (PH=7) to configure certain density mercury ion solution again adds in above-mentioned probe dispersion liquid, measures fluorescence intensity (excitation wavelength 400nm).
The external environment that this probe not only effectively reduces is to the interference of quantum dot optical property, and the distance reduced between energy donor (quantum dot) and energy acceptor (Rhodamine Derivatives), improve the energy transfer efficiency of FRET, and then enhance the susceptibility detecting mercury ion.
Accompanying drawing explanation
Fig. 1 is that the mercury ion ratio probes based on Rhodamine Derivatives and quantum dot fluorescence microballoon involved in the present invention synthesizes and detects schematic diagram.
Fig. 2 is the nuclear-magnetism figure of Rhodamine Derivatives involved in the present invention.
Fig. 3 is CdTe:Zn/SiO involved in the present invention
2the electron microscopic picture of fluorescent microsphere.
Fig. 4 is the fluorescence spectrum figure that mercury ion ratio probes involved in the present invention responds different concns mercury ion in the aqueous solution.
Fig. 5 is the fluorescence intensity ratio (I that the present invention relates to
577/ I
521) with the variation diagram of ion concentration of mercury in the aqueous solution.
Fig. 6 is that the mercury ion ratio probes that the present invention relates to is to aqueous solution intermediate ion optionally histogram.
embodiment
Embodiment 1
(1) preparation of Rhodamine Derivatives: 1.5g rhodamine B is dissolved in 30ml anhydrous methanol, add 4.8ml tri-(2-aminoethyl) amine, heated and stirred backflow at 80 DEG C, 50ml methylene dichloride and 100ml intermediate water is added after rotary evaporation of solvent, washing and filtering is spin-dried for, and obtains RHB-NH through silica gel column chromatography
2(eluent is: CH
2cl
2/ MeOH/Et
3n=40: 2: 1); By RHB-NH
2be dissolved in toluene, add 0.2ml isocyanatopropyl triethoxyl silane and 0.4ml triethylamine, stirring and refluxing at 80 DEG C, obtains Rhodamine Derivatives through silica gel column chromatography after rotary evaporation of solvent.
(2) preparation of CdTe:Zn quantum dot: 0.285g sodium borohydride and 0.32g tellurium powder are added in intermediate water 10ml, under 4 DEG C of nitrogen protections, reaction obtains sodium hydrogen telluride in 8 hours; 0.114g Cadmium chloride fine powder, 0.682g zinc chloride, 0.105ml thiohydracrylic acid are joined in 100ml intermediate water, and use sodium hydrate regulator solution PH=11, add after deoxygenation above-mentioned 0.4ml tellurium sodium cyanide be transferred in reactor put into baking oven reaction within 2 hours, obtain CdTe:Zn quantum dot.
(3) synthesis of mercury ion ratio probes: add 15ml hexanaphthene, 3.54ml Triton X-100,3.6ml n-hexyl alcohol in the CdTe:Zn quantum dot aqueous solution, lucifuge stirs, add to continue to add after 0.04ml APTES and 0.01ml TEOS has stirred after 0.2ml TEOS and 0.12ml ammoniacal liquor continue to stir and add Rhodamine Derivatives, react the mercury ion probe terminating rear eccentric cleaning and obtain based on multilayered fluorescent Nano microsphere and Rhodamine Derivatives.
The synthesis of mercury ion ratio probes and detection schematic diagram are as Fig. 1; Rhodamine Derivatives nuclear-magnetism figure is as Fig. 2; Multilayered fluorescent Nano microsphere transmission electron microscope picture is as Fig. 3.
Embodiment 2:
Mercury ion ratio probes is to the fluoroscopic examination of different concns mercury ion in the aqueous solution:
Taking 2.383gHEPES is dissolved in 800ml intermediate water, regulates PH and is settled to 1L, obtain the HEPES damping fluid of 10mmol/L after dissolving with sodium hydroxide.Mercury ion ratio probes dispersion liquid HEPES buffered soln (PH=7) of preparation is diluted by a certain percentage, use HEPES buffered soln (PH=7) to configure certain density mercury ion solution again to add in above-mentioned probe dispersion liquid, be settled to 2ml and measure fluorescence intensity (excitation wavelength 400nm).
Mercury ion ratio probes in the aqueous solution different concns mercury ion response fluorescence spectrum figure as Fig. 4; Fluorescence intensity ratio (I
577/ I
521) with ion concentration of mercury variation diagram in the aqueous solution as Fig. 5.
Embodiment 3:
Ratio probes is to the selectivity of mercury ion detecting:
Configure 1 × 10 respectively
-2the Na of mol/L
+, K
+, Ca
2+, Mg
2+, Fe
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, pb
2+, Cd
2+, Hg
2+, Al
3+deng the aqueous solution, and dilute above-mentioned solution respectively to 1 × 10
-3mol/L, 1 × 10
-4mol/L, 1 × 10
-5mol/L.Solvent is the 10mmol/L HEPES buffered soln of above-mentioned configuration.Add constant volume in ratio probes dispersion liquid and measure fluorescence intensity.
Ratio probes to the selectivity of mercury ion detecting in the aqueous solution as Fig. 6.
Claims (7)
1., based on a mercury ion ratio probes for Rhodamine Derivatives and quantum dot fluorescence microballoon, it is characterized in that: the structural formula of described Rhodamine Derivatives is:
2., based on a preparation method for the mercury ion ratio probes of Rhodamine Derivatives and quantum dot fluorescence microballoon, comprising:
(1) add in intermediate water by sodium borohydride and tellurium powder, under 4 DEG C of nitrogen protections, reaction obtains sodium hydrogen telluride in 8 hours; Wherein the mass volume ratio of sodium borohydride, tellurium powder, intermediate water is 0.285g: 0.32g: 10ml;
(2) Cadmium chloride fine powder, zinc chloride, thiohydracrylic acid are joined in intermediate water, and use sodium hydrate regulator solution PH=11, add above-mentioned tellurium sodium cyanide after deoxygenation and be transferred in reactor and put into baking oven and react; Wherein the mass volume ratio of Cadmium chloride fine powder, zinc chloride, thiohydracrylic acid, tellurium sodium cyanide, solvent is: 0.114g: 0.682g: 0.105ml: 0.4ml: 100ml;
(3) be dissolved in solvent by rhodamine B, add three (2-aminoethyl) amine, heated and stirred backflow at 80 DEG C, add methylene dichloride and intermediate water after rotary evaporation of solvent, washing and filtering is spin-dried for, and purifies, obtains RHB-NH2; Wherein the mass volume ratio of rhodamine B, three (2-aminoethyl) amine, methylene dichloride, intermediate water, solvent is: 1.5g: 4.8ml: 50ml: 100ml: 30ml;
(4) by RHB-NH
2be dissolved in solvent, add isocyanatopropyl triethoxyl silane and triethylamine, stirring and refluxing at 80 DEG C, purifying after rotary evaporation of solvent obtains Rhodamine Derivatives; Wherein RHB-NH
2, isocyanatopropyl triethoxyl silane, triethylamine mass volume ratio be: 0.2g: 0.2ml: 0.4ml;
(5) in the CdTe:Zn quantum dot aqueous solution, hexanaphthene, Triton X-100, n-hexyl alcohol is added, lucifuge stirs, add to continue to add after APTES and TEOS has stirred after TEOS and ammoniacal liquor continue to stir and add Rhodamine Derivatives, react the mercury ion ratio probes terminating rear eccentric cleaning and obtain based on multilayered fluorescent Nano microsphere and Rhodamine Derivatives.Its cyclohexane, TritonX-100, n-hexyl alcohol, TEOS, ammoniacal liquor, APTES, volume ratio are: 15ml: 3.54ml: 3.6ml: 0.2ml: 0.12ml: 0.04ml.
3. the preparation method of a kind of mercury ion ratio probes based on Rhodamine Derivatives and quantum dot fluorescence microballoon according to claim 2, is characterized in that: in described step (3), solvent is anhydrous methanol.
4. the preparation method of a kind of mercury ion ratio probes based on Rhodamine Derivatives and quantum dot fluorescence microballoon according to claim 2, is characterized in that: purify in described step (3) as silica gel column chromatography purification, eluent is: CH
2cl
2/ MeOH/Et
3n=40: 2: 1.
5. the preparation method of a kind of mercury ion ratio probes based on Rhodamine Derivatives and quantum dot fluorescence microballoon according to claim 2, is characterized in that: in described step (4), solvent is toluene.
6. the preparation method of a kind of mercury ion ratio probes based on Rhodamine Derivatives and quantum dot fluorescence microballoon according to claim 2, is characterized in that: purify in described step (4) as silica gel column chromatography purification, eluent is: CH
2cl
2/ CH
3oH=5: 1.
7. the preparation method of a kind of mercury ion ratio probes based on Rhodamine Derivatives and quantum dot fluorescence microballoon according to claim 2, is characterized in that: described step adds APTES and TEOS in (5).
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105482812A (en) * | 2015-12-18 | 2016-04-13 | 贵州大学 | Fluorescent probe reagent for concurrent selection and determination of multiple metal ions, and preparation and appliance |
| CN107892914A (en) * | 2017-12-08 | 2018-04-10 | 济南大学 | A kind of quick identification and the fluorescent microsphere preparation method for quantitatively detecting mercury ion |
| CN108218866A (en) * | 2018-04-03 | 2018-06-29 | 泰山医学院 | Pyrido benzimidazole mercury ion ratio fluorescent probe and its application |
| CN109321251A (en) * | 2017-08-01 | 2019-02-12 | 吉林师范大学 | A kind of multifunctional and composite type nanometer ratio fluorescent chemical sensor and its preparation method and application |
| CN110596072A (en) * | 2019-10-29 | 2019-12-20 | 陕西师范大学 | Ratio type fluorescent paper chip based on polyester fiber film, preparation method and application |
| CN113406049A (en) * | 2021-06-16 | 2021-09-17 | 安徽大学 | CdTe quantum dot-benzocoumarin-3-formic acid ratiometric fluorescent probe and preparation method and application thereof |
-
2014
- 2014-04-18 CN CN201410160526.6A patent/CN105018070A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105482812A (en) * | 2015-12-18 | 2016-04-13 | 贵州大学 | Fluorescent probe reagent for concurrent selection and determination of multiple metal ions, and preparation and appliance |
| CN109321251A (en) * | 2017-08-01 | 2019-02-12 | 吉林师范大学 | A kind of multifunctional and composite type nanometer ratio fluorescent chemical sensor and its preparation method and application |
| CN107892914A (en) * | 2017-12-08 | 2018-04-10 | 济南大学 | A kind of quick identification and the fluorescent microsphere preparation method for quantitatively detecting mercury ion |
| CN108218866A (en) * | 2018-04-03 | 2018-06-29 | 泰山医学院 | Pyrido benzimidazole mercury ion ratio fluorescent probe and its application |
| CN110596072A (en) * | 2019-10-29 | 2019-12-20 | 陕西师范大学 | Ratio type fluorescent paper chip based on polyester fiber film, preparation method and application |
| CN110596072B (en) * | 2019-10-29 | 2022-05-13 | 陕西师范大学 | Ratio type fluorescent paper chip based on polyester fiber film, preparation method and application |
| CN113406049A (en) * | 2021-06-16 | 2021-09-17 | 安徽大学 | CdTe quantum dot-benzocoumarin-3-formic acid ratiometric fluorescent probe and preparation method and application thereof |
| CN113406049B (en) * | 2021-06-16 | 2023-02-03 | 安徽大学 | CdTe quantum dot-benzocoumarin-3-formic acid ratiometric fluorescent probe and preparation method and application thereof |
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