CN103059835B - Phosphorodiamidate morpholino oligomer (PMO) fluorescent nanoparticle for detecting mercury ion ratio and preparation method thereof - Google Patents
Phosphorodiamidate morpholino oligomer (PMO) fluorescent nanoparticle for detecting mercury ion ratio and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a phosphorodiamidate morpholino oligomer (PMO) fluorescent nanoparticle for detecting mercury ion ratio and a preparation method thereof. The method comprises the steps of taking mesoporous silica as a carrier, and mixing with two fluorescent resonance energy transfer dye molecules; carrying out preliminary modification on an organic fluorescent molecule by a silane coupling agent, then utilizing a sol-gel chemical principle and self-assembly behaviors of a surfactant in solution as a structure-directing agent and silicon species, preparing and obtaining spherical PMO fluorescent nanoparticle by hydrolytic polycondensation between the silane coupling agent and a silicon source precursor; carrying out rhodamine dye modification on the PMO particle, and obtaining the PMO fluorescent nanoparticle for detecting the mercury ion ratio. Compared with the existing preparation route of a ratio probe, the preparation method has the main characteristics that a direct covalent bond connection between a reference signal unit and a report unit of the ratio probe is avoided; the molecular structure design of the ratio probe is simplified, and achievement of detection of different target materials is hopefully achieved by simply exchanging the reference signal unit and the report unit.
Description
Technical field
The invention belongs to advanced nano material and sensor technical field, especially relate to PMO fluorescent nano particles for mercury ion ratio test and preparation method thereof.
Background technology
Water pollutes has become global society and environmental problem.Mercury ion is as a kind of heavy metal ion, and the mankind's health has been arrived in serious threat of the water pollution causing.Mercury ion not only toxicity is very large, and be difficult for degrading, inorganic mercury ion is under the effect of microorganism, can be converted into methyl mercury, therefore it is easy to find in river and lake, can accumulate toxin, by the fishes and shrimps in lake after being eaten after food chain transforms, build up in human brain, the mankind's health and lives is caused to serious threat.Therefore, the mercury ion of environment is detected and removed have very important significance.Fluorometry is a kind of real-time, easy metal ion detection means, but this measuring method of setting up based on optical signalling variation is easy to be subject to photobleaching, sensor molecules concentration, microenvironment (the polarity of sensor molecules, pH, temperature, instrument), the impact of the luminous factors such as stability, thereby impact detects to a certain extent accuracy and precision, and ratio fluorescent method is due to the introducing of reference cell, can effectively reduce above-mentioned externalities and change the interference causing, therefore the research of mercury ion ratio probes has caused the broad interest of researchers.But the design of Ratiometric fluorescent probe and preparation process relative complex, cause Ratiometric fluorescent probe up to now to compare the development hysteresis that switching mode detects.
FRET (fluorescence resonance energy transfer) (FRET) technology is an important technology of widespread use in Modern Analytical Chemistry, and it can realize the transmitting that single wavelength excites lower multiple wavelength of fluorescence.Utilize the change of the fluorescence resonance energy transmission efficiency that metal ion causes the difference of FRET system dye molecule fluorescence intensity capability of influence can realize the ratio test to metal ion.But FRET Ratiometric fluorescent probe need to be connected the reference cell of probe and reporting unit covalency, and this needs meticulous Molecular Structure Design and complicated preparation process.In recent years, there is combinations simplification probe design that some utilize nano material and dye molecule, optimized the report of probe performance.Our seminar has reported a kind of monodispersed fluorescence PMO nanoparticle recently, by three kinds of FRET dyestuffs of different ratios are introduced to mesoporous framework, can excite lower acquisition multi-fluorescence signal (J.Am.Chem.Soc., 2012,134,8746) at single wavelength.On this basis, we can build the mercury ion ratio probes system based on FRET by two kinds of FRET fluorophores are arranged in respectively in mesoporous duct and skeleton, simplify Molecular Structure Design and the preparation process of mercury ion ratio fluorescent probe.
Summary of the invention
The object of the invention is for simplifying rate type mercury ion fluorescence probe Molecular Structure Design and preparation process, utilize the fluorescence PMO technology of preparing of having grasped, the signal reference cell of probe and reporting unit are introduced in mesoporous particle, utilized both FRET and the different respondent behaviors of mercury ion are carried out to the ratio test to mercury ion.
Object of the present invention can be achieved through the following technical solutions:
For the PMO fluorescent nano particles of mercury ion ratio test,
This nanoparticle be take mesopore silicon oxide as carrier and doped with two kinds of FRET (fluorescence resonance energy transfer) dye molecules;
Nanoparticle can send fluorescence under excited by visible light, larger overlapping owing to existing between two kinds of organic fluorescent dye molecule excitation and emission spectras introducing, can form FRET (fluorescence resonance energy transfer) dyestuff pair, therefore under single wavelength excites, can produce two kinds of fluorescent emission
Wherein a kind of FRET (fluorescence resonance energy transfer) dye molecule is responsive to mercury ion, with the variation of mercury ion in system, changes, and another kind of FRET (fluorescence resonance energy transfer) dye molecule is stable to mercury ion.
It to the FRET (fluorescence resonance energy transfer) dye molecule of mercury ion sensitivity, is the fluorescence molecule with rhodamine 6G group with amino reactive behavior.
The fluorescence molecule that is anthryl group to the stable FRET (fluorescence resonance energy transfer) dye molecule of mercury ion.
Two kinds of FRET (fluorescence resonance energy transfer) dye molecules can adopt arbitrary proportion.
As preferred embodiment, to the FRET (fluorescence resonance energy transfer) dye molecule of mercury ion sensitivity with to the mol ratio of the stable FRET (fluorescence resonance energy transfer) dye molecule of mercury ion, be 1: (2-3).
As the embodiment being more preferably, to the FRET (fluorescence resonance energy transfer) dye molecule of mercury ion sensitivity with to the mol ratio of the stable FRET (fluorescence resonance energy transfer) dye molecule of mercury ion, be 1: 2.25.
The preparation method who is used for the PMO fluorescent nano particles of mercury ion ratio test, first by silane coupling agent, anthracene is modified in advance, in recycling sol-gel chemistry principle and solution as the self-assembly behavior of tensio-active agent and the silicon species of structure directing agent, anthracene dyes and the common hydrolytie polycondensation between silicon source precursor and silane coupling agent by pre-modification prepare spherical PMO particle, again prepared PMO particle is carried out to rhodamine modification, obtain having the mesoporous PMO fluorescent nano particles of mercury ion ratio probes function.
As preferred embodiment, silicon source presoma is selected from one or more in water glass, tetraethoxy or methyl silicate;
As preferred embodiment, silane coupling agent is with amino silane coupling agent, comprises trimethoxy amine propyl silane or triethoxy amine propyl silane.
As preferred embodiment, the mol ratio between the double end silicon of described anthracene, silicon source presoma, silane coupling agent, rhodamine is (0.2-0.3): (4-5): (0.4-0.5): 0.1.
As the embodiment being more preferably, the proportionlity between the double end silicon of described anthracene, silicon source presoma, silane coupling agent, rhodamine is 0.225: 4.5: 0.427: 0.1.
As preferred embodiment, solvent is the mixing solutions of alkyl alcohol and water, and described alkyl alcohol is selected from one or more of methyl alcohol, ethanol or Virahol.
As preferred embodiment, silane coupling agent and silicon source presoma are that structure directing carries out self-assembly through tensio-active agent, and described tensio-active agent is alkyl quaternaries tensio-active agent C
ntAB, wherein n=12-18.
As preferred embodiment, when silane coupling agent and the hydrolysis of silicon source presoma, adopt basic catalyst, this basic catalyst is selected from one or more in sodium hydroxide, potassium hydroxide or strong aqua.
The particle diameter that is used for the PMO fluorescent nano particles of mercury ion ratio test is 100nm left and right.
Compared with prior art, also there is no based on FRET (fluorescence resonance energy transfer) at present the report in conjunction with the mercury ion ratio probes of PMO nanoparticle both at home and abroad, thereby the present invention by having prepared the nanoparticle with mercury ion ratio test function by organic fluorescent dye molecular dopant in PMO fluorescent nano particles, the nanoparticle of preparation has following characteristics by this method:
(1) nanoparticle has fluorescence, and under single wavelength excites, can produce two kinds of fluorescent emission;
(2) two kinds of fluorescent emission that produce, a kind of can variation with the variation of ion concentration of mercury wherein, another vary stable to ion concentration of mercury, both rate values are linear change with ion concentration of mercury;
(3) there is good biocompatibility;
(4) reaction conditions is gentle, easily repeats.
Accompanying drawing explanation
Fig. 1: (A) SEM of PMO nanoparticle figure, the SEM figure of the PMO nanoparticle that (B) rhodamine 6G is modified, (C) TEM of PMO nanoparticle figure, the TEM figure of the PMO nanoparticle that (D) rhodamine 6G is modified
Fig. 2 is the little angle XRD figure of PMO nanoparticle.(A) before dyestuff is modified, (B) after dyestuff is modified.
Fig. 3 is nitrogen adsorption desorption curve and the BJH pore size distribution curve of PMO nanoparticle, before (A) dyestuff is modified, (B) after dyestuff is modified.
Fig. 4 is different Hg
2+the fluorogram of PMO nanoparticle under concentration conditions.
Fig. 5 is the ion selectivity of PMO nanoparticle detector.
Fig. 6 is the ion competition of PMO nanoparticle detector.
Embodiment
For the PMO fluorescent nano particles of mercury ion ratio test, take mesopore silicon oxide as carrier, the right functional nano particle of the two kinds of FRET (fluorescence resonance energy transfer) (FRET) of having adulterated dyestuff, its size is 100nm left and right.
Owing to having introduced organic fluorescent dye molecule in preparation process, so this nanoparticle can send fluorescence under excited by visible light; Larger overlapping owing to existing between two kinds of organic fluorescent dye molecule excitation and emission spectras introducing, can form FRET (fluorescence resonance energy transfer) dyestuff pair, therefore under exciting, single wavelength can produce two kinds of fluorescent emission; A kind of fluorescent emission is wherein responsive, a kind of stable to mercury ion to mercury ion, and both fluorescence intensity ratio is linear changing relation with ion concentration of mercury, so this PMO particle can be used as mercury ion ratio test.
It to the FRET (fluorescence resonance energy transfer) dye molecule of mercury ion sensitivity, is the fluorescence molecule with rhodamine 6G group with amino reactive behavior, can change with the variation of mercury ion in system, the fluorescence molecule that is anthryl group to the stable FRET (fluorescence resonance energy transfer) dye molecule of mercury ion, stable to mercury ion, both fluorescence intensity ratio is linear changing relation with the variation of ion concentration of mercury, thereby can carry out ratio test to the mercury ion of system.
In addition, PMO particle has high degree of order structure, and organic molecule is distributed in the skeleton of duct, can obtain 100% modification of maximum; The organic group being connected on the skeleton of duct can not block mesoporous; Owing to thering is orderly meso-hole structure, can in water, realize the mercury ion detecting of lower concentration.
Two kinds of FRET (fluorescence resonance energy transfer) dye molecules can adopt arbitrary proportion, in actual preparation engineering, to the FRET (fluorescence resonance energy transfer) dye molecule of mercury ion sensitivity with to the mol ratio of the stable FRET (fluorescence resonance energy transfer) dye molecule of mercury ion, be 1: 2.25.
The preparation method who is used for the PMO fluorescent nano particles of mercury ion ratio test, first by silane coupling agent, anthracene is modified in advance, in recycling sol-gel chemistry principle and solution as the self-assembly behavior of tensio-active agent and the silicon species of structure directing agent, anthracene dyes and the common hydrolytie polycondensation between silicon source precursor and silane coupling agent by pre-modification prepare spherical PMO particle, again prepared PMO particle is carried out to rhodamine modification, obtain having the mesoporous PMO fluorescent nano particles of mercury ion ratio probes function.
The silicon source presoma that can adopt in embodiment is selected from one or more in water glass, tetraethoxy or methyl silicate, adopts successfully self-assembly formation PMO nanoparticle of these silicon source presomas.
The silane coupling agent that can adopt in embodiment for amino silane coupling agent, comprises trimethoxy amine propyl silane or triethoxy amine propyl silane, adopts these silane coupling agents can be successfully at the nanoparticle surface modified amino of PMO.
Proportionlity between the double end silicon of the anthracene adopting in embodiment, silicon source presoma, silane coupling agent, rhodamine is 0.225: 4.5: 0.427: 0.1.
Solvent is the mixing solutions of alkyl alcohol and water, and described alkyl alcohol is selected from one or more of methyl alcohol, ethanol or Virahol.
Silane coupling agent and silicon source presoma are that structure directing carries out self-assembly through tensio-active agent, and tensio-active agent is alkyl quaternaries tensio-active agent C
ntAB, wherein n=12-18.
When silane coupling agent and the hydrolysis of silicon source presoma, adopt basic catalyst, this basic catalyst is selected from one or more in sodium hydroxide, potassium hydroxide or strong aqua.
The particle diameter of the PMO fluorescent nano particles for mercury ion ratio test preparing through aforesaid method is 100nm left and right, and aperture is between 2-5nm, and organic molecule is distributed in the skeleton of duct, can obtain 100% modification of maximum; The organic group being connected on the skeleton of duct can not block mesoporous; And there is orderly meso-hole structure, and can in water, realize the mercury ion detecting of lower concentration, use convenient.
The present invention relates to preparation method and the Performance Detection of the mercury ion ratio fluorescent probe based on fluorescence mesoporous PMO nanoparticle, the signal reference cell of this ratio probes and reporting unit be the energy of a pair of FRET (fluorescence resonance energy transfer) dyestuff to acceptor molecule, both lay respectively in the hole wall and duct of mesoporous particle.Signal reference cell is by first anthryl dyestuff being modified into double end silylation molecule in advance with silane coupling agent, then introduces in mesoporous wall with the method for other silicon source copolycondensation; Signal reporting unit is rhodamine lactam derivatives, by with mesoporous hole inwall on introduce in advance-NH
2the mode of reacting and being anchored with covalency is introduced in duct.Signal reporting unit in hole wall is to mercury ion inertia, and can cause the ring-opening reaction of dye molecule lactan group in rhodamine lactan dye molecule in duct with after mercury ion complexing, " co " type response that the fluorescence of dyestuff grows out of nothing, and further cause the variation of fluorescence resonance energy transmission efficiency between anthracene chromophoric group in itself and hole wall, thereby form, the Ratio-type of mercury ion is detected.Compare with the syntheti c route of existing ratio probes, principal feature is by the signal reference of FRET (fluorescence resonance energy transfer) type ratio probes and reporting unit are arranged in respectively in mesoporous hole wall and duct, avoided direct covalent linkage between two kinds of unit to connect, this route has been simplified the Molecular Structure Design of ratio probes, by being expected to, by providing for simple replacement of signal reference cell and reporting unit, realizes the detection to different target material.
Below by embodiment, the present invention is further illustrated, and its object is only better to understand content of the present invention but not limits the scope of the invention:
Embodiment 1
(1) 9,10-dichloromethyl anthracene (0.548g, 2mmol) is dissolved in anhydrous acetonitrile (40mL) solution, then adds anhydrous K
2cO
3(1.09g, 8mmol) and APTS (0.96mL, 4mmol), this mixing solutions refluxes 48 hours under nitrogen protection.After reaction finishes, solution is cooled to room temperature, removes organic solvent, residuum is purified with column chromatography, and (silicagel column, eluent is CH
2cl
2), obtain faint yellow transparent oily liquid (0.20g, productive rate is 15%).
(2) preparation of PMO nanoparticle is improved by one
method.First, get cetyl trimethylammonium bromide (CTAB, 0.2g, 5.5 * 10
-4mol) and NaOH (0.7mL, 2M) in flask, add bi-distilled water (DDW) 100mL.Mixed solution is stirred 15 minutes, be then heated to 70 ℃, add subsequently 1.0mL (0.94g, 4.5mmol) tetraethyl orthosilicate (TEOS), the anthracene of the two silylations of 140mg (0.225mmol) and 0.1mL (0.427mmol) APTS.After 1 minute, add 1.0mL ethyl acetate, and gained mixture is stirred 30 seconds to then aging 4 hours at 70 ℃.When solution is cooled to after room temperature, throw out is collected by filtration, and water and washing with alcohol several.
(3) extraction removes tensio-active agent: get sample 50mg in step 2 and be distributed in 5ml ethanol, add 50mg Glacial acetic acid ammonium, return stirring reaction 1h, 12000rpm centrifugation, ethanol and washing 4 times, 60 ℃ of vacuum-drying 6h.
(4) rhodamine-6G hydrazine derivative 3 is to prepare according to former work.Get 0.0468g (0.1mmol) compound 3 in the ethanolic soln (8mL) of the PMO of APTS modification nanoparticle (0.03g).Add 2 Glacial acetic acid, under 90 ℃ of lower magnetic forces stir, reflux 24 hours.After having reacted, solid product is used methylene dichloride and washing with alcohol repeatedly, and under vacuum, is dried 5 hours at 60 ℃.
Intermediate product and the product for preparing are tested, as shown in Figure 1, wherein, A is the SEM figure of PMO nanoparticle, and B is the SEM figure of the PMO nanoparticle of rhodamine 6G modification, C is the TEM figure of PMO nanoparticle, D is the TEM figure of the PMO nanoparticle of rhodamine 6G modification, passable by above-mentioned SEM and TEM photo, the pattern that the nanoparticle of preparation has had, particle is single dispersion, uniform particle diameter.
Fig. 2 is the little angle XRD figure of PMO nanoparticle.A is the situation before rhodamine is modified, and B is the situation after rhodamine is modified, and all has orderly meso-hole structure as shown in Figure 2 before and after the PMO Nanoparticle Modified of preparation.
Fig. 3 is nitrogen adsorption desorption curve and the BJH pore size distribution curve of PMO nanoparticle, and A is the situation before rhodamine is modified, and B is the situation after rhodamine is modified, and Fig. 3 illustrates the N before and after PMO Nanoparticle Modified
2adsorption/desorption curve is all typical IV type curve, clearly shows its mesoporous characteristic.
Embodiment 2
The material that utilization prepares detects mercury ion, different Hg
2+under concentration conditions, the fluorogram of PMO nanoparticle as shown in Figure 4.(from bottom to fixed point, Hg
2+concentration is (1 * 10
-8m～1 * 10
-4m), as known in the figure, in the time of in adding R6G/Anth-PMO (50mg/L) the Hepes damping fluid that the mercury ion of different amounts is 7.0 in pH, the fluorescent emission intensity at 550nm place strengthens gradually, and Fig. 4 illustrates that PMO nanoparticle detector has good detection performance to mercury ion.
Fig. 5 is the ion selectivity of PMO nanoparticle detector, and as we know from the figure, a key character of the PMO nanoparticle after modification is that it is to Hg
2+show highly selective.After adding, most of competitive ions do not cause any obvious change in fluorescence.Yet, work as Hg
2+after joining in the aqueous solution, this nanoparticle shows obvious fluorescent emission at 550nm, illustrates that this probe has good selectivity to mercury ion.
Fig. 6 is the ion competition of PMO nanoparticle detector, and as we know from the figure, Fig. 6 illustrates at Hg
2+during with the coexisting of other metal ions, PMO particle still shows very strong fluorescent emission.Illustrate that the prepared PMO nanoparticle of this chapter has good immunity from interference, to Hg
2+specific recognition ability is very high.
Embodiment 3
PMO fluorescent nano particles for mercury ion ratio test be take mesopore silicon oxide as carrier and doped with two kinds of FRET (fluorescence resonance energy transfer) dye molecules, wherein a kind of FRET (fluorescence resonance energy transfer) dye molecule is responsive to mercury ion, variation with mercury ion in system changes, and another kind of FRET (fluorescence resonance energy transfer) dye molecule is stable to mercury ion.
Nanoparticle can send fluorescence under UV, visible light optical excitation, larger overlapping owing to existing between two kinds of organic fluorescent dye molecule excitation and emission spectras introducing, can form FRET (fluorescence resonance energy transfer) dyestuff pair, therefore under single wavelength excites, can produce two kinds of fluorescent emission.In the present embodiment, it to the FRET (fluorescence resonance energy transfer) dye molecule of mercury ion sensitivity, is the fluorescence molecule with rhodamine 6G group with amino reactive behavior, the fluorescence molecule that is anthryl group to the stable FRET (fluorescence resonance energy transfer) dye molecule of mercury ion, to the FRET (fluorescence resonance energy transfer) dye molecule of mercury ion sensitivity with to the mol ratio of the stable FRET (fluorescence resonance energy transfer) dye molecule of mercury ion, be 1: 2.
The preparation method who is used for the PMO fluorescent nano particles of mercury ion ratio test, comprises the following steps:
(1) first by trimethoxy amine propyl silane, the double end silicon of anthracene is modified in advance, in the solution of recycling sol-gel chemistry principle and methyl alcohol as the tensio-active agent C of structure directing agent
12the self-assembly behavior of TAB and silicon species, between anthracene dyes by pre-modification and water glass and trimethoxy amine propyl silane, under the catalysis of basic catalyst sodium hydroxide, common hydrolytie polycondensation prepares and take mesopore silicon oxide as carrier, doped with the spherical PMO fluorescent nano particles to the stable FRET (fluorescence resonance energy transfer) dye molecule of mercury ion;
(2) utilize rhodamine to react with the amino group of particle surface, in whole reaction system, mol ratio between the double end silicon of anthracene, water glass, trimethoxy amine propyl silane, rhodamine is 0.3: 5: 0.5: 0.1, obtaining particle diameter is 100nm left and right, for the PMO fluorescent nano particles of mercury ion ratio test.
Embodiment 4
PMO fluorescent nano particles for mercury ion ratio test be take mesopore silicon oxide as carrier and doped with two kinds of FRET (fluorescence resonance energy transfer) dye molecules, wherein a kind of FRET (fluorescence resonance energy transfer) dye molecule is responsive to mercury ion, variation with mercury ion in system changes, and another kind of FRET (fluorescence resonance energy transfer) dye molecule is stable to mercury ion.
Nanoparticle can send fluorescence under UV, visible light optical excitation, larger overlapping owing to existing between two kinds of organic fluorescent dye molecule excitation and emission spectras introducing, can form FRET (fluorescence resonance energy transfer) dyestuff pair, therefore under single wavelength excites, can produce two kinds of fluorescent emission.In the present embodiment, it to the FRET (fluorescence resonance energy transfer) dye molecule of mercury ion sensitivity, is the fluorescence molecule with rhodamine 6G group with amino reactive behavior, the fluorescence molecule that is anthryl group to the stable FRET (fluorescence resonance energy transfer) dye molecule of mercury ion, to the FRET (fluorescence resonance energy transfer) dye molecule of mercury ion sensitivity with to the mol ratio of the stable FRET (fluorescence resonance energy transfer) dye molecule of mercury ion, be 1: 3.
The preparation method who is used for the PMO fluorescent nano particles of mercury ion ratio test, comprises the following steps:
(1) first by triethoxy amine propyl silane, the double end silicon of anthracene is modified in advance, in the aqueous solution of recycling sol-gel chemistry principle and methyl alcohol and ethanol as the tensio-active agent C of structure directing agent
18the self-assembly behavior of TAB and silicon species, between anthracene dyes by pre-modification and tetraethoxy and triethoxy amine propyl silane, under the catalysis of basic catalyst sodium hydroxide, common hydrolytie polycondensation prepares and take mesopore silicon oxide as carrier, doped with the spherical PMO fluorescent nano particles to the stable FRET (fluorescence resonance energy transfer) dye molecule of mercury ion;
(2) utilize rhodamine to react with the amino group of particle surface, in whole reaction system, mol ratio between the double end silicon of anthracene, tetraethoxy, triethoxy amine propyl silane, rhodamine is 0.2: 4: 0.4: 0.1, obtaining particle diameter is 100nm left and right, for the PMO fluorescent nano particles of mercury ion ratio test.
Claims (8)
1. for the PMO fluorescent nano particles of mercury ion ratio test, it is characterized in that,
This nanoparticle be take mesopore silicon oxide as carrier and doped with two kinds of FRET (fluorescence resonance energy transfer) dye molecules;
A kind of FRET (fluorescence resonance energy transfer) dye molecule is responsive to mercury ion, with the variation of mercury ion in system, changes, and another kind of FRET (fluorescence resonance energy transfer) dye molecule is stable to mercury ion, and two kinds of FRET (fluorescence resonance energy transfer) dye molecules can adopt arbitrary proportion;
It to the FRET (fluorescence resonance energy transfer) dye molecule of mercury ion sensitivity, is the fluorescence molecule with rhodamine 6G group with amino reactive behavior, and the energy acceptor while shifting as fluorescence resonance resonance energy, the fluorescence molecule that is anthryl group to the stable FRET (fluorescence resonance energy transfer) dye molecule of mercury ion, and the energy while shifting as fluorescence resonance resonance energy is to body.
2. the PMO fluorescent nano particles for mercury ion ratio test according to claim 1, it is characterized in that, to the FRET (fluorescence resonance energy transfer) dye molecule of mercury ion sensitivity with to the mol ratio of the stable FRET (fluorescence resonance energy transfer) dye molecule of mercury ion, be 1:(2-3).
As described in any one in claim 1-2 for the preparation method of the PMO fluorescent nano particles of mercury ion ratio test, it is characterized in that, the method adopts following steps:
(1) the double end silicon by anthracene and silicon source presoma and silane coupling agent hydrolytie polycondensation in solvent obtain take mesopore silicon oxide as carrier, doped with the spherical PMO fluorescent nano particles to the stable FRET (fluorescence resonance energy transfer) dye molecule of mercury ion;
(2) utilize rhodamine to react with the amino group of particle surface, obtain the PMO fluorescent nano particles for mercury ion ratio test.
4. according to claim 3 for the preparation method of the PMO fluorescent nano particles of mercury ion ratio test, it is characterized in that,
Described silicon source presoma is selected from one or more in water glass, tetraethoxy or methyl silicate;
Described silane coupling agent is with amino silane coupling agent, comprises trimethoxy amine propyl silane or triethoxy amine propyl silane.
According to described in claim 3 or 4 for the preparation method of the PMO fluorescent nano particles of mercury ion ratio test, it is characterized in that, the mol ratio between the double end silicon of described anthracene, silicon source presoma, silane coupling agent, rhodamine is (0.2-0.3): (4-5): (0.4-0.5): 0.1.
6. according to claim 3 for the preparation method of the PMO fluorescent nano particles of mercury ion ratio test, it is characterized in that, described solvent is the mixing solutions of alkyl alcohol and water, and described alkyl alcohol is selected from one or more of methyl alcohol, ethanol or Virahol.
7. according to claim 3 for the preparation method of the PMO fluorescent nano particles of mercury ion ratio test, it is characterized in that, described silane coupling agent and silicon source presoma are that structure directing carries out self-assembly through tensio-active agent, and described tensio-active agent is alkyl quaternaries tensio-active agent C
ntAB, wherein n=12-18.
8. according to claim 3 for the preparation method of the PMO fluorescent nano particles of mercury ion ratio test, it is characterized in that, when described silane coupling agent and the hydrolysis of silicon source presoma, adopt basic catalyst, this basic catalyst is selected from one or more in sodium hydroxide, potassium hydroxide or strong aqua.
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