CN103952147A - Fluorescent magnetic nanoparticle for hypochlorous acid detection and synthetic method thereof - Google Patents

Fluorescent magnetic nanoparticle for hypochlorous acid detection and synthetic method thereof Download PDF

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CN103952147A
CN103952147A CN201410178241.5A CN201410178241A CN103952147A CN 103952147 A CN103952147 A CN 103952147A CN 201410178241 A CN201410178241 A CN 201410178241A CN 103952147 A CN103952147 A CN 103952147A
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hypochlorous acid
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hypochlorous
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CN103952147B (en
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张祯
邓成权
刘小龙
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Xian Jiaotong University
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Xian Jiaotong University
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Abstract

The invention discloses a fluorescent magnetic nanoparticle for hypochlorous acid detection and a synthetic method thereof. The synthetic method comprises the following steps: preparing a ferroferric oxide magnetic nanoparticle as a magnetic core material by adopting a solvent thermal method, coating the outer part of the magnetic core with a layer of nonporous silicon dioxide and a layer of mesoporous silicon dioxide in sequence by adopting a sol-gel method, and finally covalently modifying a magnetic mesoporous material obtained in the previous two steps with an organic fluorescent molecule capable of specifically identifying hypochlorous acid through a silane coupling agent, thus obtaining the fluorescent magnetic nanoparticle for the hypochlorous acid detection. The nanoparticle is simple in a preparation process and low in cost; the detection of high sensitivity and high selectivity of the hypochlorous acid can be realized by utilizing the remarkable enhancement of a fluorescent signal of the nanoparticle before and after recognition; and the magnetic control and separation of the magnetic nanoparticle can be realized by additionally arranging a magnetic field. The fluorescent magnetic nanoparticle and the synthetic method thereof have an important application prospect in the fields of visual tracing and imaging of the hypochlorous acid in living organisms, quantitative detection of hypochlorous acid in environmental water, clearing and the like.

Description

A kind of fluorescence magnetic particle and synthetic method thereof detecting for hypochlorous acid
Technical field
The invention belongs to nano material and chemical sensor field, be specifically related to a kind of fluorescence magnetic particle and synthetic method thereof detecting for hypochlorous acid.
Background technology
Life science and environment science has become the common hot research field of paying close attention to, the whole world, for the research of various biological phenomenas and environmental pollutant monitoring method, is paid attention to day by day widely.Hypochlorous acid (HOCl) is a kind of strong oxidizer, can in active bio body He in water treatment procedure, play anti-microbial effect.In vivo, hypochlorous acid is the important active oxygen species of a class (ROS), in many processes with important physiology and biological significance, plays critical effect.But excessive hypochlorous formation meeting induce tissue damage, causes the even generation of the serial disease such as cancer of arteriosclerosis, sacroiliitis.In daily life, hypochlorous acid, because sterilization effect is good, cheap and easy to use, has been widely used as disinfection of tap water agent.But the hypochlorous acid solution pungency of high density is strong, injury respiratory system, in Yi Yushui, organism reaction generates the serious carcinogenic substance such as chloroform, tetracol phenixin, and the mankind's health is existed to potential harm.Therefore, development has the hypochlorous acid detection method of high sensitivity and highly selective, in fields such as the relevant biological action research of hypochlorous acid and environmental monitorings, has important using value.
At present, detect hypochlorous method and mainly contain Sulfothiorine volumetry (HG/T2498-93), o-tolidine colorimetric method (GB5750-85) and tetramethyl benzidine (TMB) colorimetry etc.But these detection method poor selectivity, are easily disturbed, and in application aspect, have considerable restraint.In addition, some organic fluorescence probes of development in recent years go out good susceptibility, selectivity and biocompatibility (Org.Lett.2013,15:878-881 to hypochlorous acid detection display; J.Am.Chem.Soc.2012,134:1200-1211; Chem.Eur.J.2012,18:2700-2706; Chem.Commun.2011,47:12691-12693).But these detection methods on the one hand related organic fluorescence probe building-up process complexity are loaded down with trivial details, on the other hand detection means and function singleness.
Summary of the invention
The object of the invention is to overcome the shortcoming of above-mentioned prior art, a kind of fluorescence magnetic particle and synthetic method thereof detecting for hypochlorous acid is provided, the process of the synthetic fluorescence magnetic particle of the method is simple, and synthetic fluorescence magnetic particle can be quick, highly sensitive and highly selective realize hypochlorous detection.
For achieving the above object, the chemical expression of the fluorescence magnetic particle detecting for hypochlorous acid of the present invention is:
Fe 3O 4@mSiO 2@nSi?O 2@Rh6GH
Wherein, Fe 3o 4for magnetic nano particle daughter nucleus, mSiO 2for atresia silicon dioxide layer, nSiO 2for meso-porous titanium dioxide silicon layer, Rh6GH is the hypochlorous organic fluorescence molecule of specific recognition, and Rh6GH is for passing through the product of propyl trimethoxy silicane covalent coupling behind outer mesoporous silicon oxide surface, and the structure of Rh6GH is:
Accordingly, the present invention also provides a kind of synthetic method of the fluorescence magnetic particle detecting for hypochlorous acid, comprises the following steps:
A.Fe 3o 4synthetic:
Take a certain amount of FeCl 36H 2o, anhydrous sodium acetate and ethylene glycol, wherein, FeCl 36H 2the ratio of O and anhydrous sodium acetate and ethylene glycol is 1.0mmol: 8-10mmol: 8-9mL, then by FeCl 36H 2o and anhydrous sodium acetate are dissolved in ethylene glycol, mix and are placed in Hydrothermal Synthesis still, be cooled to room temperature, then go out black precipitate by centrifugation after its reaction completes, and then, after washing and drying under reduced pressure, obtain Fe 3o 4;
B.Fe 3o 4@mSiO 2@nSiO 2synthetic:
1) take the Fe that a certain amount of step a obtains 3o 4, then by dilute hydrochloric acid to Fe 3o 4carry out supersound process, then in the mixing solutions a forming with the ammoniacal liquor that to be dispersed to by ethanol, deionized water and massfraction after deionized water wash be 25%, wherein, Fe in mixing solutions a 3o 4, ethanol, deionized water and ammoniacal liquor ratio be 1g: 300-600mL: 75-150mL: 1-3mL, then in mixing solutions a, drip tetraethoxy, wherein, Fe in tetraethoxy and mixing solutions a 3o 4mass ratio be 1: 2-6, after at room temperature stirring, with magnet, isolate product A, product A, after washing, obtains Fe 3o 4@mSiO 2;
2) get a certain amount of step 1) Fe that obtains 3o 4@mSiO 2, then by Fe 3o 4@mSiO 2in the mixing solutions b that the ammoniacal liquor that to be dispersed to by ethanol, deionized water, massfraction be 25% and cetyl trimethylammonium bromide form, wherein, Fe in mixing solutions b 3o 4@mSiO 2, ethanol, deionized water, ammoniacal liquor and cetyl trimethylammonium bromide ratio be 1g: 300-600mL: 240-480mL: 3.5-8mL: 2-4g, and then drip tetraethoxy in mixing solutions b, wherein, Fe in tetraethoxy and mixing solutions b 3o 4mass ratio be 1-4: 1, and at room temperature stir, then by magnet, isolate product B, product B, through washing and drying under reduced pressure, then is mixed dried product B with the ethanol of ammonium nitrate and 95%, obtain mixture c, wherein, in mixture c, the ratio of product B, ammonium nitrate and ethanol is 1g: 0.2-0.4g: 80-120mL, after stirring, with magnet, isolates product C, product C, after washing and drying under reduced pressure, obtains Fe 3o 4@mSiO 2@nSiO 2;
C. the meso-porous titanium dioxide silicon face of magnetic nano-particle is introduced silane coupling reagent:
Take the Fe that a certain amount of 3-r-chloropropyl trimethoxyl silane and step b obtain 3o 4@mSiO 2@nSiO 2, wherein, Fe 3o 4@mSiO 2@nSiO 2with the ratio of 3-r-chloropropyl trimethoxyl silane be 1g: 0.2-0.6mL, then by Fe 3o 4@mSiO 2@nSiO 2be scattered in toluene with 3-r-chloropropyl trimethoxyl silane, reflux and cooling after, by magnet, isolate product D, product D is after washing and drying under reduced pressure, the meso-porous titanium dioxide silicon face that completes magnetic nano-particle is introduced silane coupling reagent;
D. the hypochlorous organic fluorescence molecule of specific recognition Rh6GHN's is synthetic:
Take ethanolic soln and a hydrazine hydrate of a certain amount of rhodamine 6G, again a hydrazine hydrate is added drop-wise in the ethanolic soln of rhodamine 6G, obtain mixing solutions d, wherein, in mixing solutions d, the ratio of rhodamine 6G, ethanol and a hydrazine hydrate is 1.0g: 20-30mL: 2-4mL, mixing solutions d through reflux and cooling after, filter out pink precipitation, and then by after pink washing of precipitate and being dried, obtain the hypochlorous organic fluorescence molecule of specific recognition Rh6GHN;
Magnetic nano-particle synthetic e. with photoluminescent property:
Take the hypochlorous organic fluorescence molecule of the specific recognition Rh6GHN that dried product D that a certain amount of step c obtains and steps d obtain, wherein, the mass ratio of the hypochlorous organic fluorescence molecule of product D and specific recognition Rh6GHN is 1: 0.8-1.2, then product D and the hypochlorous organic fluorescence molecule of specific recognition Rh6GHN are scattered in toluene, after reflux, with magnet, isolate product E, product E is after washing and drying under reduced pressure, with acetonitrile-water mixing solutions, reflux again, remove the hypochlorous organic fluorescence molecule of excessive specific recognition Rh6GHN, then by magnet, isolate product F, product F is after washing and drying under reduced pressure, obtain Fe 3o 4@mSiO 2@nSiO 2@Rh6GH.
Temperature in step a in Hydrothermal Synthesis still is 200 ℃, and the time of reaction is 4-12h;
Absolute ethanol washing is passed through in black precipitate described in step a;
Step b 1) in time of at room temperature stirring be 4-8h;
Step b 1) in product A by ethanol and deionized water wash;
Step b 2) in time of at room temperature stirring be 4-8h;
Step b 2) in product B by ethanol and deionized water wash;
Step b 2) in magnet, isolate product C concrete operations after stirring and be, with magnet, isolate product C stir 20-40min under the condition of 60 ℃ after;
Step b 2) in product C deionized water wash;
In step c, the time of reflux is 18-30h;
In step c, product D is passed through toluene wash;
In steps d, the time of reflux is 2-4h;
In step e, the time of reflux is 8-12h;
In step e, product E passes through toluene wash;
In step e, with the time that acetonitrile-water mixing solutions refluxes, be 2-4h;
In step e, product F, after washing, is placed in vacuum-drying 12-18h under the condition of 60 ℃.
The present invention has following beneficial effect:
The fluorescence magnetic particle preparation flow detecting for hypochlorous acid of the present invention is simple, cost is low, and the fluorescence of the fluorescence magnetic particle detecting for hypochlorous acid of the present invention is very weak, but can optionally react with hypochlorous acid, produces obvious enhancement effect of fluorescence; And speed of response is fast, can demonstrate at short notice strong fluorescence, highly sensitive, when being 2 μ M, hypochlorous concentration also can produce obvious fluorescence response; In addition, the fluorescence magnetic particle detecting for hypochlorous acid of the present invention has very high selectivity, under the condition only existing at hypochlorous acid, just can demonstrate obvious fluorescent signal, and the metal ion that other are common and active specy all do not produce interference.And because the fluorescence magnetic particle detecting for hypochlorous acid of the present invention has magnetic kernel, therefore can realize its magnetic control system separated with magnetic by externally-applied magnetic field.Finally, the fluorescence magnetic particle detecting for hypochlorous acid of the present invention is a kind of multifunctional material with fluorescence identification receptor and magnetic kernel, the fields such as the visual spike imaging of hypochlorous acid in living organisms and the hypochlorous acid detection by quantitative in ambient water and removing have important application prospect, in fields such as the relevant biological action research of hypochlorous acid and environmental monitorings, have important using value.
Accompanying drawing explanation
Fig. 1 is Fe 3o 4the X-ray powder diffraction of crystal;
Fig. 2 (a) is Fe 3o 4@mSiO 2@nSiO 2scanning electron microscope image;
Fig. 2 (b) is Fe 3o 4scanning electron microscope image;
Fig. 3 (a) is Fe 3o 4@mSiO 2@nSiO 2images of transmissive electron microscope;
Fig. 3 (b) is Fe 3o 4images of transmissive electron microscope;
Fig. 4 is Fe 3o 4and Fe 3o 4@mSiO 2@nSiO 2magnetic hysteresis loop;
Fig. 5 is Fe 3o 4@mSiO 2@nSiO 2magnetic resolution photo under additional the action of a magnetic field in 1 minute;
Fig. 6 (a) is Fe 3o 4@mSiO 2@nSiO 2n 2adsorption-desorption thermoisopleth;
Fig. 6 (b) is Fe 3o 4@mSiO 2@nSiO 2pore size distribution;
Fig. 7 is Fe 3o 4@mSiO 2@nSiO 2@Rh6GH detects hypochlorous fluorescence emission spectrum;
Fig. 8 (a) is Fe 3o 4@mSiO 2@nSiO 2the fluorescence emission spectrum of@Rh6GH and the effect of different concns hypochlorous acid;
Fig. 8 (b) is Fe 3o 4@mSiO 2@nSiO 2the working curve of the relative intensity of fluorescence of@Rh6GH and hypochlorous acid effect to hypochlorous acid concentration;
Fig. 9 is Fe 3o 4@mSiO 2@nSiO 2@Rh6GH detects hypochlorous fluorescence intensity over time;
Figure 10 is Fe 3o 4@mSiO 2@nSiO 2the fluorescence response intensity of@Rh6GH to hypochlorous acid and various common metal ion;
Figure 11 is Fe 3o 4@mSiO 2@nSiO 2the fluorescence response intensity of@Rh6GH to hypochlorous acid and various common active species.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail:
The chemical expression of the fluorescence magnetic particle detecting for hypochlorous acid of the present invention is:
Fe 3O 4@mSiO 2@nSiO 2@Rh6GH
Wherein, Fe 3o 4for magnetic nano particle daughter nucleus, mSiO 2for atresia silicon dioxide layer, nSiO 2for meso-porous titanium dioxide silicon layer, Rh6GH is the hypochlorous organic fluorescence molecule of specific recognition, and Rh6GH is for passing through the product of propyl trimethoxy silicane covalent coupling behind outer mesoporous silicon oxide surface, and the structure of Rh6GH is:
With reference to figure 1, Fe 3o 4magnetic nano-particle has the inverse spinel structure of standard, with reference to figure 2 (a) and Fig. 2 (b), Fe 3o 4for mean diameter approximates the spherical of 300nm, Fe 3o 4@mSiO 2@nSiO 2for mean diameter approximates the spherical of 600nm, and Fe 3o 4@mSiO 2@nSiO 2compare Fe 3o 4surface more smooth; Shown by being progressively coated the magnetic mesoporous silicon materials that process is prepared the nucleocapsid structure with conformation of rules feature visual result shown in Fig. 3 (a) and Fig. 3 (b); With reference to figure 4, area that magnetic hysteresis loop encloses is very little, Fe 3o 4and Fe 3o 4@mSiO 2@nSiO 2saturation magnetization be respectively 76.20emu/g and 48.61emu/g, remanent magnetism is respectively 4.40emu/g and 5.36emu/g, coercive force is respectively 530e and 730e, has shown the feature of superparamagnetism; With reference to figure 5, under additional the action of a magnetic field, the Fe being dispersed in water 3o 4@mSiO 2@nSiO 2can in 1 minute, complete fast separation; With reference to figure 6 (a) and Fig. 6 (b), Fe 3o 4@mSiO 2@nSiO 2bET specific surface area be 93.08m 2/ g, BJH mean pore size is 2.8nm, belongs to mesoporous scope.
Embodiment mono-
The synthetic method of the fluorescence magnetic particle detecting for hypochlorous acid of the present invention comprises the following steps:
A.Fe 3o 4synthetic:
Take a certain amount of FeCl 36H 2o, anhydrous sodium acetate and ethylene glycol, wherein, FeCl 36H 2the ratio of O and anhydrous sodium acetate and ethylene glycol is 1.0mmol: 10mmol: 9mL, then by FeCl 36H 2o and anhydrous sodium acetate are dissolved in ethylene glycol, mixing and being placed on temperature is to react 12h in the Hydrothermal Synthesis still of 200 ℃, is cooled to room temperature, then goes out black precipitate by centrifugation after its reaction completes, then after absolute ethanol washing and drying under reduced pressure, obtain Fe 3o 4;
B.Fe 3o 4@mSiO 2@nSiO 2synthetic:
1) take the Fe that a certain amount of step a obtains 3o 4, then by dilute hydrochloric acid to Fe 3o 4carry out supersound process, then in the mixing solutions a forming with the ammoniacal liquor that to be dispersed to by ethanol, deionized water and massfraction after deionized water wash be 25%, wherein, Fe in mixing solutions a 3o 4, ethanol, deionized water and ammoniacal liquor ratio be 1g: 400mL: 100mL: 3mL, then in mixing solutions a, drip tetraethoxy, wherein, Fe in tetraethoxy and mixing solutions a 3o 4mass ratio be 1: 2, with magnet, isolate product A after at room temperature stirring 8h, product A, after ethanol and deionized water wash, obtains Fe 3o 4@mSiO 2;
2) get a certain amount of step 1) Fe that obtains 3o 4@mSiO 2, then by Fe 3o 4@mSiO 2in the mixing solutions b that the ammoniacal liquor that to be dispersed to by ethanol, deionized water, massfraction be 25% and cetyl trimethylammonium bromide form, wherein, Fe in mixing solutions b 3o 4@mSiO 2, ethanol, deionized water, ammoniacal liquor and cetyl trimethylammonium bromide ratio be 1g: 400mL: 300mL: 8mL: 2g, and then drip tetraethoxy in mixing solutions b, wherein, Fe in tetraethoxy and mixing solutions b 3o 4mass ratio be 1: 1, and at room temperature stir 8h, then by magnet, isolate product B, product B is through ethanol and deionized water wash drying under reduced pressure, more dried product B is mixed with the ethanol of ammonium nitrate and 95%, obtain mixture c, wherein, in mixture c, the ratio of product B, ammonium nitrate and ethanol is 1g: 0.4g: 100mL, with magnet isolates product C after stirring 40min under the condition of 60 ℃, product C, after deionized water wash and drying under reduced pressure, obtains Fe 3o 4@mSiO 2@nSiO 2;
C. the meso-porous titanium dioxide silicon face of magnetic nano-particle is introduced silane coupling reagent:
Take the Fe that a certain amount of 3-r-chloropropyl trimethoxyl silane and step b obtain 3o 4@mSiO 2@nSiO 2, wherein, Fe 3o 4@mSiO 2@nSiO 2with the ratio of 3-r-chloropropyl trimethoxyl silane be 1g: 0.6mL, then by Fe 3o 4@mSiO 2@nSiO 2be scattered in toluene with 3-r-chloropropyl trimethoxyl silane, reflux 18h and cooling after, by magnet, isolate product D, product D is after toluene wash and drying under reduced pressure, the meso-porous titanium dioxide silicon face that completes magnetic nano-particle is introduced silane coupling reagent;
D. the hypochlorous organic fluorescence molecule of specific recognition Rh6GHN's is synthetic:
Take ethanolic soln and a hydrazine hydrate of a certain amount of rhodamine 6G, again a hydrazine hydrate is added drop-wise in the ethanolic soln of rhodamine 6G, obtain mixing solutions d, wherein, in mixing solutions d, the ratio of rhodamine 6G, ethanol and a hydrazine hydrate is 1.0g: 30mL: 2mL, mixing solutions d through reflux 4h and cooling after, filter out pink precipitation, and then by after pink washing of precipitate and being dried, obtain the hypochlorous organic fluorescence molecule of specific recognition Rh6GHN;
Magnetic nano-particle synthetic e. with photoluminescent property:
Take the hypochlorous organic fluorescence molecule of the specific recognition Rh6GHN that dried product D that a certain amount of step c obtains and steps d obtain, wherein, the mass ratio of the hypochlorous organic fluorescence molecule of product D and specific recognition Rh6GHN is 1: 1.2, then product D and the hypochlorous organic fluorescence molecule of specific recognition Rh6GHN are scattered in toluene, after reflux 8h, with magnet, isolate product E, product E is after toluene wash and drying under reduced pressure, use again acetonitrile-water mixing solutions backflow 2h, remove the hypochlorous organic fluorescence molecule of excessive specific recognition Rh6GHN, then by magnet, isolate product F, product F is after washing, be placed in vacuum-drying 12h under the condition of 60 ℃, obtain Fe 3o 4@mSiO 2@nSiO 2@Rh6GH.
Embodiment bis-
The synthetic method of the fluorescence magnetic particle detecting for hypochlorous acid of the present invention comprises the following steps:
A.Fe 3o 4synthetic:
Take a certain amount of FeCl 36H 2o, anhydrous sodium acetate and ethylene glycol, wherein, FeCl 36H 2the ratio of O and anhydrous sodium acetate and ethylene glycol is 1.0mmol: 8mmol: 8mL, then by FeCl 36H 2o and anhydrous sodium acetate are dissolved in ethylene glycol, and mixing and being placed on temperature is to react 8h in the Hydrothermal Synthesis still of 200 ℃, is cooled to room temperature, then goes out black precipitate by centrifugation after its reaction completes, and then, after absolute ethanol washing and drying under reduced pressure, obtains Fe 3o 4;
B.Fe 3o 4@mSiO 2@nSiO 2synthetic:
1) take the Fe that a certain amount of step a obtains 3o 4, then by dilute hydrochloric acid to Fe 3o 4carry out supersound process, then in the mixing solutions a forming with the ammoniacal liquor that to be dispersed to by ethanol, deionized water and massfraction after deionized water wash be 25%, wherein, Fe in mixing solutions a 3o 4, ethanol, deionized water and ammoniacal liquor ratio be 1g: 600mL: 75mL: 1mL, then in mixing solutions a, drip tetraethoxy, wherein, Fe in tetraethoxy and mixing solutions a 3o 4mass ratio be 1: 6, with magnet, isolate product A after at room temperature stirring 6h, product A, after ethanol and deionized water wash, obtains Fe 3o 4@mSiO 2;
2) get a certain amount of step 1) Fe that obtains 3o 4@mSiO 2, then by Fe 3o 4@mSiO 2in the mixing solutions b that the ammoniacal liquor that to be dispersed to by ethanol, deionized water, massfraction be 25% and cetyl trimethylammonium bromide form, wherein, Fe in mixing solutions b 3o 4@mSiO 2, ethanol, deionized water, ammoniacal liquor and cetyl trimethylammonium bromide ratio be 1g: 600mL: 240mL: 3.5mL: 4g, and then drip tetraethoxy in mixing solutions b, wherein, Fe in tetraethoxy and mixing solutions b 3o 4mass ratio be 2: 1, and at room temperature stir 5h, then by magnet, isolate product B, product B is through ethanol and deionized water wash drying under reduced pressure, more dried product B is mixed with the ethanol of ammonium nitrate and 95%, obtain mixture c, wherein, in mixture c, the ratio of product B, ammonium nitrate and ethanol is 1g: 0.3g: 120mL, with magnet isolates product C after stirring 20min under the condition of 60 ℃, product C, after deionized water wash and drying under reduced pressure, obtains Fe 3o 4@mSiO 2@nSiO 2;
C. the meso-porous titanium dioxide silicon face of magnetic nano-particle is introduced silane coupling reagent:
Take the Fe that a certain amount of 3-r-chloropropyl trimethoxyl silane and step b obtain 3o 4@mSiO 2@nSiO 2, wherein, Fe 3o 4@mSiO 2@nSiO 2with the ratio of 3-r-chloropropyl trimethoxyl silane be 1g: 0.4mL, then by Fe 3o 4@mSiO 2@nSiO 2be scattered in toluene with 3-r-chloropropyl trimethoxyl silane, reflux 25h and cooling after, by magnet, isolate product D, product D is after toluene wash and drying under reduced pressure, the meso-porous titanium dioxide silicon face that completes magnetic nano-particle is introduced silane coupling reagent;
D. the hypochlorous organic fluorescence molecule of specific recognition Rh6GHN's is synthetic:
Take ethanolic soln and a hydrazine hydrate of a certain amount of rhodamine 6G, again a hydrazine hydrate is added drop-wise in the ethanolic soln of rhodamine 6G, obtain mixing solutions d, wherein, in mixing solutions d, the ratio of rhodamine 6G, ethanol and a hydrazine hydrate is 1.0g: 25mL: 3mL, mixing solutions d through reflux 3h and cooling after, filter out pink precipitation, and then by after pink washing of precipitate and being dried, obtain the hypochlorous organic fluorescence molecule of specific recognition Rh6GHN;
Magnetic nano-particle synthetic e. with photoluminescent property:
Take the hypochlorous organic fluorescence molecule of the specific recognition Rh6GHN that dried product D that a certain amount of step c obtains and steps d obtain, wherein, the mass ratio of the hypochlorous organic fluorescence molecule of product D and specific recognition Rh6GHN is 1: 1, then product D and the hypochlorous organic fluorescence molecule of specific recognition Rh6GHN are scattered in toluene, after reflux 10h, with magnet, isolate product E, product E is after toluene wash and drying under reduced pressure, use again acetonitrile-water mixing solutions backflow 3h, remove the hypochlorous organic fluorescence molecule of excessive specific recognition Rh6GHN, then by magnet, isolate product F, product F is after washing, be placed in vacuum-drying 15h under the condition of 60 ℃, obtain Fe 3o 4@mSiO 2@nSiO 2@Rh6GH.
Embodiment tri-
The synthetic method of the fluorescence magnetic particle detecting for hypochlorous acid of the present invention comprises the following steps:
A.Fe 3o 4synthetic:
Take a certain amount of FeCl 36H 2o, anhydrous sodium acetate and ethylene glycol, wherein, FeCl 36H 2the ratio of O and anhydrous sodium acetate and ethylene glycol is 1.0mmol: 9mmol: 8.5mL, then by FeCl 36H 2o and anhydrous sodium acetate are dissolved in ethylene glycol, and mixing and being placed on temperature is to react 4h in the Hydrothermal Synthesis still of 200 ℃, is cooled to room temperature, then goes out black precipitate by centrifugation after its reaction completes, and then, after absolute ethanol washing and drying under reduced pressure, obtains Fe 3o 4;
B.Fe 3o 4@mSiO 2@nSiO 2synthetic:
1) take the Fe that a certain amount of step a obtains 3o 4, then by dilute hydrochloric acid to Fe 3o 4carry out supersound process, then in the mixing solutions a forming with the ammoniacal liquor that to be dispersed to by ethanol, deionized water and massfraction after deionized water wash be 25%, wherein, Fe in mixing solutions a 3o 4, ethanol, deionized water and ammoniacal liquor ratio be 1g: 300mL: 150mL: 2.5mL, then in mixing solutions a, drip tetraethoxy, wherein, the Fe in tetraethoxy and mixing solutions a 3o 4with mass ratio be 1: 2, with magnet, isolate product A after at room temperature stirring 4h, product A, after ethanol and deionized water wash, obtains Fe 3o 4@mSiO 2;
2) get a certain amount of step 1) Fe that obtains 3o 4@mSiO 2, then by Fe 3o 4@mSiO 2in the mixing solutions b that the ammoniacal liquor that to be dispersed to by ethanol, deionized water, massfraction be 25% and cetyl trimethylammonium bromide form, wherein, Fe in mixing solutions b 3o 4@mSiO 2, ethanol, deionized water, ammoniacal liquor and cetyl trimethylammonium bromide ratio be 1g: 300mL: 480mL: 5mL: 3g, and then drip tetraethoxy in mixing solutions b, wherein, Fe in tetraethoxy and mixing solutions b 3o 4mass ratio be 4: 1, and at room temperature stir 4h, then by magnet, isolate product B, product B is through ethanol and deionized water wash drying under reduced pressure, more dried product B is mixed with the ethanol of ammonium nitrate and 95%, obtain mixture c, wherein, in mixture c, the ratio of product B, ammonium nitrate and ethanol is 1g: 0.2g: 80mL, with magnet isolates product C after stirring 30min under the condition of 60 ℃, product C, after deionized water wash and drying under reduced pressure, obtains Fe 3o 4@mSiO 2@nSiO 2;
C. the meso-porous titanium dioxide silicon face of magnetic nano-particle is introduced silane coupling reagent:
Take the Fe that a certain amount of 3-r-chloropropyl trimethoxyl silane and step b obtain 3o 4@mSiO 2@nSiO 2, wherein, Fe 3o 4@mSiO 2@nSiO 2with the ratio of 3-r-chloropropyl trimethoxyl silane be 1g: 0.2mL, then by Fe 3o 4@mSiO 2@nSiO 2be scattered in toluene with 3-r-chloropropyl trimethoxyl silane, reflux 30h and cooling after, by magnet, isolate product D, product D is through toluene wash and drying under reduced pressure, the meso-porous titanium dioxide silicon face that completes magnetic nano-particle is introduced silane coupling reagent;
D. the hypochlorous organic fluorescence molecule of specific recognition Rh6GHN's is synthetic:
Take ethanolic soln and a hydrazine hydrate of a certain amount of rhodamine 6G, again a hydrazine hydrate is added drop-wise in the ethanolic soln of rhodamine 6G, obtain mixing solutions d, wherein, in mixing solutions d, the ratio of rhodamine 6G, ethanol and a hydrazine hydrate is 1.0g: 20mL: 4mL, mixing solutions d through reflux 2h and cooling after, filter out pink precipitation, and then by after pink washing of precipitate and being dried, obtain the hypochlorous organic fluorescence molecule of specific recognition Rh6GHN;
Magnetic nano-particle synthetic e. with photoluminescent property:
Take the hypochlorous organic fluorescence molecule of the specific recognition Rh6GHN that dried product D that a certain amount of step c obtains and steps d obtain, wherein, the mass ratio of the hypochlorous organic fluorescence molecule of product D and specific recognition Rh6GHN is 1: 0.8, then product D and the hypochlorous organic fluorescence molecule of specific recognition Rh6GHN are scattered in toluene, after reflux 12h, with magnet, isolate product E, product E is after toluene wash and drying under reduced pressure, use again acetonitrile-water mixing solutions backflow 4h, remove the hypochlorous organic fluorescence molecule of excessive specific recognition Rh6GHN, then by magnet, isolate product F, product F is after washing, be placed in vacuum-drying 18h under the condition of 60 ℃, obtain Fe 3o 4@mSiO 2@nSiO 2@Rh6GH.
Embodiment tetra-
The synthetic method of the fluorescence magnetic particle detecting for hypochlorous acid of the present invention comprises the following steps:
A.Fe 3o 4synthetic:
Take a certain amount of FeCl 36H 2o, anhydrous sodium acetate and ethylene glycol, wherein, FeCl 36H 2the ratio of O and anhydrous sodium acetate and ethylene glycol is 1.0mmol: 8.5mmol: 8.7mL, then by FeCl 36H 2o and anhydrous sodium acetate are dissolved in ethylene glycol, and mixing and being placed on temperature is to react 6h in the Hydrothermal Synthesis still of 200 ℃, is cooled to room temperature, then goes out black precipitate by centrifugation after its reaction completes, and then, after absolute ethanol washing and drying under reduced pressure, obtains Fe 3o 4;
B.Fe 3o 4@mSiO 2@nSiO 2synthetic:
1) take the Fe that a certain amount of step a obtains 3o 4, then by dilute hydrochloric acid to Fe 3o 4carry out supersound process, then in the mixing solutions a forming with the ammoniacal liquor that to be dispersed to by ethanol, deionized water and massfraction after deionized water wash be 25%, wherein, Fe in mixing solutions a 3o 4, ethanol, deionized water and ammoniacal liquor ratio be 1g: 400mL: 130mL: 2.5mL, then in mixing solutions a, drip tetraethoxy, wherein, Fe in tetraethoxy and mixing solutions a 3o 4mass ratio be 1: 3, with magnet, isolate product A after at room temperature stirring 5h, product A, after ethanol and deionized water wash, obtains Fe 3o 4@mSiO 2;
2) get a certain amount of step 1) Fe that obtains 3o 4@mSiO 2, then by Fe 3o 4@mSiO 2in the mixing solutions b that the ammoniacal liquor that to be dispersed to by ethanol, deionized water, massfraction be 25% and cetyl trimethylammonium bromide form, wherein, Fe in mixing solutions b 3o 4@mSiO 2, ethanol, deionized water, ammoniacal liquor and cetyl trimethylammonium bromide ratio be 1g: 500mL: 400mL: 7mL: 2.5g, and then drip tetraethoxy in mixing solutions b, wherein, Fe in tetraethoxy and mixing solutions b 3o 4mass ratio be 3: 1, and at room temperature stir 7h, then by magnet, isolate product B, product B is through ethanol and deionized water wash drying under reduced pressure, more dried product B is mixed with the ethanol of ammonium nitrate and 95%, obtain mixture c, wherein, in mixture c, the ratio of product B, ammonium nitrate and ethanol is 1g: 0.25g: 90mL, with magnet isolates product C after stirring 25min under the condition of 60 ℃, product C, after deionized water wash and drying under reduced pressure, obtains Fe 3o 4@mSiO 2@nSiO 2;
C. the meso-porous titanium dioxide silicon face of magnetic nano-particle is introduced silane coupling reagent:
Take the Fe that a certain amount of 3-r-chloropropyl trimethoxyl silane and step b obtain 3o 4@mSiO 2@nSiO 2, wherein, Fe 3o 4@mSiO 2@nSiO 2with the ratio of 3-r-chloropropyl trimethoxyl silane be 1g: 0.3mL, then by Fe 3o 4@mSiO 2@nSiO 2be scattered in toluene with 3-r-chloropropyl trimethoxyl silane, reflux 25h and cooling after, by magnet, isolate product D, product D is through toluene wash and drying under reduced pressure, the meso-porous titanium dioxide silicon face that completes magnetic nano-particle is introduced silane coupling reagent;
D. the hypochlorous organic fluorescence molecule of specific recognition Rh6GHN's is synthetic:
Take ethanolic soln and a hydrazine hydrate of a certain amount of rhodamine 6G, again a hydrazine hydrate is added drop-wise in the ethanolic soln of rhodamine 6G, obtain mixing solutions d, wherein, in mixing solutions d, the ratio of rhodamine 6G, ethanol and a hydrazine hydrate is 1.0g: 27mL: 2.5mL, mixing solutions d through reflux 3.5h and cooling after, filter out pink precipitation, and then by after pink washing of precipitate and being dried, obtain the hypochlorous organic fluorescence molecule of specific recognition Rh6GHN;
Magnetic nano-particle synthetic e. with photoluminescent property:
Take the hypochlorous organic fluorescence molecule of the specific recognition Rh6GHN that dried product D that a certain amount of step c obtains and steps d obtain, wherein, the mass ratio of the hypochlorous organic fluorescence molecule of product D and specific recognition Rh6GHN is 1: 1.1, then product D and the hypochlorous organic fluorescence molecule of specific recognition Rh6GHN are scattered in toluene, after reflux 11h, with magnet, isolate product E, product E is after toluene wash and drying under reduced pressure, use again acetonitrile-water mixing solutions backflow 2.5h, remove the hypochlorous organic fluorescence molecule of excessive specific recognition Rh6GHN, then by magnet, isolate product F, product F is after washing, be placed in vacuum-drying 14h under the condition of 60 ℃, obtain Fe 3o 4@mSiO 2@nSiO 2@Rh6GH.
Wherein, the proton nmr spectra of the hypochlorous organic fluorescence molecule of specific recognition Rh6GHN and carbon-13 nmr spectra measurement result are as follows:
Nuclear magnetic resonance hydrogen spectruming determining: 1h NMR (400MHz, CDCl 3), δ (ppm): 7.96 (m, 1H), 7.46-7.43 (m, 2H), 7.06 (m, 1H), 6.40 (s, 2H), 6.26 (s, 2H), 3.59 (br, 4H), 3.22 (q, J=7.2Hz, 4H), 1.92 (s, 6H), 1.32 (t, J=7.2Hz, 6H).
Carbon-13 nmr spectra is measured: 13c NMR (100MHz, CDCl 3), δ (ppm): 166.1,152.2,151.7,147.4,132.5,129.8,128.0,127.6,123.7,122.9,117.9,105.0,96.9,66.0,38.3,16.6,14.7.
Mass spectroscopy: m/z429.2[M+H] +, 451.2[M+Na] +.
Experiment 1:Fe 3o 4@mSiO 2@nSiO 2@Rh6GH carries out fluorometric analysis to hypochlorous acid:
By Fe 3o 4@mSiO 2@nSiO 2@Rh6GH is dispersed in acetonitrile, is mixed with the storing solution of 1.0g/L, the Fe that is 1.0g/L by 10 μ L concentration 3o 4@mSiO 2@nSiO 2the acetonitrile solution of@Rh6GH joins in 2mL centrifuge tube, and then toward the acetonitrile that adds 90 μ L in centrifuge tube, the clorox standardized solution that adds again different amounts, and with phosphoric acid salt (pH7.4) the buffered soln constant volume of 10mM to 1mL, make hypochlorous concentration in system be respectively 0-150 μ M.Under room temperature, act on after 30 seconds, it is in 1.0cm, the volume quartz colorimetric utensil that is 1.0mL that sample is positioned over to optical path, arranges that to excite and launch slit width be 5.0nm, and photomultiplier transit tube voltage is 700V, with the wavelength of 500nm, excites, and measures its fluorescence emission spectrum.
Fig. 7 is 0.01g/L Fe 3o 4@mSiO 2@nSiO 2fluorescence emission spectrum after@Rh6GH and 100 μ M hypochlorous acid effects.
Fig. 8 (a) is 0.01g/L Fe 3o 4@mSiO 2@nSiO 2fluorescence emission spectrum after hypochlorous acid effect in@Rh6GH and 0-150 μ M concentration range; Fig. 8 (b) be hypochlorous acid concentration within the scope of 0-150 μ M, 0.01g/LFe 3o 4@mSiO 2@nSiO 2working curve after@Rh6GH and hypochlorous acid effect, at the relative intensity of fluorescence at 550nm fluorescent emission wavelength place to hypochlorous acid concentration.
Shown in Fig. 7, result shows, the PBS damping fluid that the volume fraction 10% of take is 7.4 as acetonitrile and pH is made solvent, the fluorescence of fluorescence magnetic particle of 0.01g/L own is very weak, but with the hypochlorous acid effect of 100 μ mol/L after 30 seconds, fluorescent signal can significantly be detected, shown that the hypochlorous organic fluorescence probe of specific recognition Rh6GH has been connected to magnetic mesoporous material surface, successfully synthesizes Fe 3o 4@mSiO 2@nSiO 2@Rh6GH.
Shown in Fig. 8 (a) and Fig. 8 (b), result shows, the PBS damping fluid that the volume fraction 10% of take is 7.4 as acetonitrile and pH is made solvent, under the experiment condition that the fluorescence magnetic particle concentration detecting for hypochlorous acid is 0.01g/L, when being 2 μ M, hypochlorous acid concentration also can produce obvious fluorescence response.And along with the increase of hypochlorous acid concentration, the intensity of fluorescence emission spectrum peak is corresponding increase also.But when hypochlorous acid concentration is increased to 150 μ M from 120 μ M, peak value starts to reduce (having occurred fluorescent quenching phenomenon).Fig. 8 (b) has provided hypochlorous acid concentration within the scope of 0-150 μ M, and fluorescence magnetic nano material is at the relative intensity of fluorescence at 550nm place.Working curve presents and first rises to maximum, and then downward trend a little.The linearity range that hypochlorous acid is detected is 0-50 μ M, detects and is limited to 3.9 μ M.The visible fluorescence magnetic particle detecting for hypochlorous acid of the present invention detects and has higher susceptibility hypochlorous acid.
Experiment 2:Fe 3o 4@mSiO 2@nSiO 2the kinetics of@Rh6GH and hypochlorous acid effect:
The Fe that is 1.0g/L by 10 μ L concentration 3o 4@mSiO 2@nSiO 2the acetonitrile solution of@Rh6GH joins in 2mL centrifuge tube, then the acetonitrile that adds 90 μ L, and with 10mM phosphoric acid salt (pH7.4) buffered soln constant volume to 1mL, being positioned over optical path is 1.0em again, volume is in the quartz colorimetric utensil of 1.0mL, setting excites and launches slit width is 5.0nm, photomultiplier transit tube voltage is 700V, add again appropriate clorox standardized solution, making hypochlorous concentration in system is 50 μ M, after hypochlorous acid adds, after fully mixing fast, with the wavelength of 500nm, excite immediately, measure the time dependent curve of transmitted wave strong point fluorescence intensity of 550nm.
Fig. 9 is 0.01g/L Fe 3o 4@mSiO 2@nSiO 2@Rh6GH detects 50 μ M hypochlorous acid, at the relative intensity of fluorescence of 550nm transmitted wave strong point over time.
Shown in Fig. 9, result shows, Fe 3o 4@mSiO 2@nSiO 2the speed of@Rh6GH and hypochlorous acid effect is very fast, after mixing, will produce stronger fluorescent signal at once.Therefore the moment that is equilibrated at of detecting reaches, and along with the increase of time, fluorescence intensity does not almost increase.
Experiment 3:Fe 3o 4@mSiO 2@nSiO 2the selectivity research of@Rh6GH to hypochlorous acid and various common metal ion:
The Fe that is 1.0g/L by 10 μ L concentration 3o 4@mSiO 2@nSiO 2the acetonitrile solution of@Rh6GH joins in 2mL centrifuge tube, then the acetonitrile that adds 90 μ L, add respectively more appropriate clorox standardized solution or the standardized solution of each metal ion species, making the concentration of hypochlorous acid in system or other each metal ion species is 100 μ M, then use 10mM phosphoric acid salt (pH7.4) buffered soln constant volume to 1mL, under room temperature, contain hypochlorous solution effects 30 seconds, other solution effects that contain metal ion 10 minutes, respectively sample being positioned over to optical path is again 1.0em, volume is in the quartz colorimetric utensil of 1.0mL, setting excites and launches slit width is 5.0nm, photomultiplier transit tube voltage is 700V, with the wavelength of 500nm, excite, measure its fluorescence emission spectrum.
Figure 10 is 0.01g/L Fe 3o 4@mSiO 2@nSiO 2the fluorescence response intensity of@Rh6GH to 100 μ M hypochlorous acid and various common metal ion.
Experiment 4:Fe 3o 4@mSiO 2@nSiO 2the selectivity research of@Rh6GH to hypochlorous acid and various common active species:
Various active species are prepared according to the methods below:
HOCl:NaOCl standardized solution at room temperature adds.
ROO .: by 2,2 '-azo (2-methyl-propyl amidine) dihydrochloride generates.
NO .: by cyanogen iron (III) SODIUMNITRATE two hydrates, generated.
ONOO -: the EDTA of the azanol that contains 0.01mol/L, the sodium hydroxide of 0.5mol/L and 0.001mol/L is vigorous stirring 4-5h under aerobic conditions, adds afterwards a small amount of MnO 2powder is to remove the H producing in reaction soln 2o 2, after solution filter, being kept at-18 ℃, the concentration of peroxynitrite is measured (ε=1670L.mol by the uv-absorbing at 302nm -1.cm -1) (Talanta2002,57:883-890).
H 2o 2: H 2o 2standardized solution at room temperature adds.
.oH: iron protochloride adds the H of 10 times of concentration 2o 2in.
1o 2: by ONOO -h with 10 times of concentration 2o 2preparation (FEBS Lett.1994,355:287-289).
The Fe that is 1.0g/L by 10 μ L concentration 3o 4@mSiO 2@nSiO 2the acetonitrile solution of@Rh6GH joins in 2mL centrifuge tube, again toward the acetonitrile that adds 90 μ L in centrifuge tube, add respectively more appropriate clorox standardized solution or the standardized solution of various active species, making the concentration of hypochlorous acid in system or other active species is 100 μ M, then use 10mM phosphoric acid salt (pH7.4) buffered soln constant volume to 1mL, under room temperature, contain hypochlorous solution effects 30 seconds, contain .oH, ONOO -with 1o 2solution effects 10 minutes, contain NO .solution effects 30 minutes, contain H 2o 2and ROO .solution effects 60 minutes.In the quartz colorimetric utensil that respectively sample to be positioned over to optical path again and to be 1.0cm, volume be 1.0mL, arrange that to excite and launch slit width be 5.0nm, photomultiplier transit tube voltage is 700V, with the wavelength of 500nm, excites, and measures its fluorescence emission spectrum.
Figure 11 is 0.01g/L Fe 3o 4@mSiO 2@nSiO 2the fluorescence response intensity of@Rh6GH to 100 μ M hypochlorous acid and various common active species.
Shown in Figure 10 and Figure 11, result shows, Fe 3o 4@mSiO 2@nSiO 2@Rh6GH almost without any response, shows obvious fluorescent signal under the condition only existing at hypochlorous acid to various common metal ions and active specy, and therefore, this fluorescence magnetic particle has very high selectivity to hypochlorous acid.

Claims (7)

1. the fluorescence magnetic particle detecting for hypochlorous acid, is characterized in that, the chemical expression of the described fluorescence magnetic particle detecting for hypochlorous acid is:
Fe 3O 4@mSiO 2@nSiO 2@Rh6GH
Wherein, Fe 3o 4for magnetic nano particle daughter nucleus, mSiO 2for atresia silicon dioxide layer, nSiO 2for meso-porous titanium dioxide silicon layer, Rh6GH is the hypochlorous organic fluorescence molecule of specific recognition, and Rh6GH is for passing through the product of propyl trimethoxy silicane covalent coupling behind outer mesoporous silicon oxide surface, and the structure of Rh6GH is:
2. a synthetic method for the fluorescence magnetic particle detecting for hypochlorous acid, is characterized in that, comprises the following steps:
A.Fe 3o 4synthetic:
Take a certain amount of FeCl 36H 2o, anhydrous sodium acetate and ethylene glycol, wherein, FeCl 36H 2the ratio of O and anhydrous sodium acetate and ethylene glycol is 1.0mmol: 8-10mmol: 8-9mL, then by FeCl 36H 2o and anhydrous sodium acetate are dissolved in ethylene glycol, mix and are placed in Hydrothermal Synthesis still, be cooled to room temperature, then go out black precipitate by centrifugation after its reaction completes, and then, after washing and drying under reduced pressure, obtain Fe 3o 4;
B.Fe 3o 4@mSiO 2@nSiO 2synthetic:
1) take the Fe that a certain amount of step a obtains 3o 4, then by dilute hydrochloric acid to Fe 3o 4carry out supersound process, then in the mixing solutions a forming with the ammoniacal liquor that to be dispersed to by ethanol, deionized water and massfraction after deionized water wash be 25%, wherein, Fe in mixing solutions a 3o 4, ethanol, deionized water and ammoniacal liquor ratio be lg: 300-600mL: 75-150mL: 1-3mL, then in mixing solutions a, drip tetraethoxy, wherein, Fe in tetraethoxy and mixing solutions a 3o 4mass ratio be 1: 2-6, after at room temperature stirring, with magnet, isolate product A, product A, after washing, obtains Fe 3o 4@mSiO 2;
2) get a certain amount of step 1) Fe that obtains 3o 4@mSiO 2, then by Fe 3o 4@mSiO 2in the mixing solutions b that the ammoniacal liquor that to be dispersed to by ethanol, deionized water, massfraction be 25% and cetyl trimethylammonium bromide form, wherein, Fe in mixing solutions b 3o 4@mSiO 2, ethanol, deionized water, ammoniacal liquor and cetyl trimethylammonium bromide ratio be 1g: 300-600mL: 240-480mL: 3.5-8mL: 2-4g, and then drip tetraethoxy in mixing solutions b, wherein, Fe in tetraethoxy and mixing solutions b 3o 4mass ratio be 1-4: 1, and at room temperature stir, then by magnet, isolate product B, product B, through washing and drying under reduced pressure, then is mixed dried product B with the ethanol of ammonium nitrate and 95%, obtain mixture c, wherein, in mixture c, the ratio of product B, ammonium nitrate and ethanol is 1g: 0.2-0.4g: 80-120mL, after stirring, with magnet, isolates product C, product C, after washing and drying under reduced pressure, obtains Fe 3o 4@mSiO 2@nSiO 2;
C. the meso-porous titanium dioxide silicon face of magnetic nano-particle is introduced silane coupling reagent:
Take the Fe that a certain amount of 3-r-chloropropyl trimethoxyl silane and step b obtain 3o 4@mSiO 2@nSiO 2, wherein, Fe 3o 4@mSiO 2@nSiO 2with the ratio of 3-r-chloropropyl trimethoxyl silane be 1g: 0.2-0.6mL, then by Fe 3o 4@mSiO 2@nSiO 2be distributed in toluene with 3-r-chloropropyl trimethoxyl silane, reflux and cooling after, by magnet, isolate product D, product D is after washing and drying under reduced pressure, the meso-porous titanium dioxide silicon face that completes magnetic nano-particle is introduced silane coupling reagent;
D. the hypochlorous organic fluorescence molecule of specific recognition Rh6GHN's is synthetic:
Take ethanolic soln and a hydrazine hydrate of a certain amount of rhodamine 6G, again a hydrazine hydrate is added drop-wise in the ethanolic soln of rhodamine 6G, obtain mixing solutions d, wherein, in mixing solutions d, the ratio of rhodamine 6G, ethanol and a hydrazine hydrate is 1.0g: 20-30mL: 2-4mL, mixing solutions d through reflux and cooling after, filter out pink precipitation, and then by after pink washing of precipitate and being dried, obtain the hypochlorous organic fluorescence molecule of specific recognition Rh6GHN;
Magnetic nano-particle synthetic e. with photoluminescent property:
Take the hypochlorous organic fluorescence molecule of the specific recognition Rh6GHN that dried product D that a certain amount of step c obtains and steps d obtain, wherein, the mass ratio of the hypochlorous organic fluorescence molecule of product D and specific recognition Rh6GHN is 1:0.8-1.2, then product D and the hypochlorous organic fluorescence molecule of specific recognition Rh6GHN are scattered in toluene, after reflux, with magnet, isolate product E, product E is after washing and drying under reduced pressure, with acetonitrile-water mixing solutions, reflux again, remove the hypochlorous organic fluorescence molecule of excessive specific recognition Rh6GHN, then by magnet, isolate product F, product F is after washing and drying under reduced pressure, obtain Fe 3o 4@mSiO 2@nSiO 2@Rh6GH.
3. the synthetic method of the fluorescence magnetic particle detecting for hypochlorous acid according to claim 2, is characterized in that,
Temperature in step a in Hydrothermal Synthesis still is 200 ℃, and the time of reaction is 4-12h;
Absolute ethanol washing is passed through in black precipitate described in step a.
4. the synthetic method of the fluorescence magnetic particle detecting for hypochlorous acid according to claim 2, is characterized in that,
Step b 1) in time of at room temperature stirring be 4-8h;
Step b 1) in product A by ethanol and deionized water wash;
Step b 2) in time of at room temperature stirring be 4-8h;
Step b 2) in product B by ethanol and deionized water wash;
Step b 2) in magnet, isolate product C concrete operations after stirring and be, with magnet, isolate product C stir 20-40min under the condition of 60 ℃ after;
Step b 2) in product C deionized water wash.
5. the synthetic method of the fluorescence magnetic particle detecting for hypochlorous acid according to claim 2, is characterized in that,
In step c, the time of reflux is 18-30h;
In step c, product D is passed through toluene wash.
6. the synthetic method of the fluorescence magnetic particle detecting for hypochlorous acid according to claim 2, is characterized in that,
In steps d, the time of reflux is 2-4h.
7. the synthetic method of the fluorescence magnetic particle detecting for hypochlorous acid according to claim 2, is characterized in that,
In step e, the time of reflux is 8-12h;
In step e, product E passes through toluene wash;
In step e, with the return time that acetonitrile-water mixing solutions refluxes, be 2-4h;
In step e, after product F washing, be placed in vacuum-drying 12-18h at 60 ℃.
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103730223A (en) * 2013-12-31 2014-04-16 深圳先进技术研究院 Superparamagnetic nanospheres and preparation method thereof
CN104949948A (en) * 2015-06-18 2015-09-30 中国农业科学院农业质量标准与检测技术研究所 Magnetic fluorescent nano material, and preparation method and application of material
CN105950132A (en) * 2016-04-20 2016-09-21 吉林大学 Amphiphilic silane-coated water-soluble composite nano-material and application thereof
CN106466488A (en) * 2016-09-27 2017-03-01 复旦大学附属华山医院 There is ultra-fine magnetic core-shell nano material and its preparation and the application of tumor cell targeting
CN107286173A (en) * 2017-05-17 2017-10-24 西北大学 Rhodol analog derivatives and its preparation method and application
CN107790075A (en) * 2016-09-06 2018-03-13 南京理工大学 A kind of magnetic mesoporous SiO of nucleocapsid shell structure2The preparation method of nano-particle
CN109126726A (en) * 2018-09-29 2019-01-04 江苏齐耀生物科技有限公司 A kind of mesoporous magnetic particle preparation method
CN109439314A (en) * 2018-12-07 2019-03-08 武汉工程大学 The preparation method of the magnetic Nano fluorescence probe of specific recognition Fe (III)
CN110231316A (en) * 2019-04-26 2019-09-13 山西医科大学 The preparation of bimodal nano-probe and its label and imaging to mescenchymal stem cell
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101302220A (en) * 2007-05-08 2008-11-12 中国科学院化学研究所 N-benzoyl rhodamine B hydrazine, preparation and use thereof
CN101670107A (en) * 2009-09-29 2010-03-17 哈尔滨工程大学 Multifunctional nuclear shell structure drug carrier material and preparation method thereof
WO2010120013A1 (en) * 2009-04-16 2010-10-21 이화여자대학교 산학협력단 Novel rhodamine derivative and hypochlorous acid detecting sensor comprising same
CN102433113A (en) * 2011-09-23 2012-05-02 吉林大学 Method for doping amino-reactive dye in silicon dioxide nano-particles
CN102908992A (en) * 2012-10-18 2013-02-06 中国科学院宁波材料技术与工程研究所 Bifunctional material for detecting and adsorbing mercury ions as well as synthesizing method and application of same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101302220A (en) * 2007-05-08 2008-11-12 中国科学院化学研究所 N-benzoyl rhodamine B hydrazine, preparation and use thereof
WO2010120013A1 (en) * 2009-04-16 2010-10-21 이화여자대학교 산학협력단 Novel rhodamine derivative and hypochlorous acid detecting sensor comprising same
CN101670107A (en) * 2009-09-29 2010-03-17 哈尔滨工程大学 Multifunctional nuclear shell structure drug carrier material and preparation method thereof
CN102433113A (en) * 2011-09-23 2012-05-02 吉林大学 Method for doping amino-reactive dye in silicon dioxide nano-particles
CN102908992A (en) * 2012-10-18 2013-02-06 中国科学院宁波材料技术与工程研究所 Bifunctional material for detecting and adsorbing mercury ions as well as synthesizing method and application of same

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
YI ZHOU等，: "Rhodamine-Modifi ed Upconversion Nanophosphors for Ratiometric Detection of Hypochlorous Acid in Aqueous Solution and Living Cells", 《SMALL》 *
ZHEN ZHANG，等: "Sensitive and selective off–on rhodamine hydrazide fluorescent chemosensor for hypochlorous acid detection and bioimaging", 《TALANTA》 *
张祯，等: "《罗丹明类次氯酸荧光探针的设计合成及其识别性能的研究》", 《中国化学会第27届学术年会第03分会场摘要集》 *

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103730223B (en) * 2013-12-31 2017-10-13 深圳先进技术研究院 Super-paramagnetism nano ball and preparation method thereof
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CN104949948B (en) * 2015-06-18 2017-09-12 中国农业科学院农业质量标准与检测技术研究所 A kind of magnetic flourescent nano material for magnetic and preparation method and application
CN105950132A (en) * 2016-04-20 2016-09-21 吉林大学 Amphiphilic silane-coated water-soluble composite nano-material and application thereof
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CN107790075B (en) * 2016-09-06 2020-12-11 南京理工大学 Magnetic mesoporous SiO with core-shell structure2Process for preparing nanoparticles
CN106466488A (en) * 2016-09-27 2017-03-01 复旦大学附属华山医院 There is ultra-fine magnetic core-shell nano material and its preparation and the application of tumor cell targeting
CN107286173B (en) * 2017-05-17 2020-01-07 扶风慈缘生物科技有限公司 Rhodol derivative and preparation method and application thereof
CN107286173A (en) * 2017-05-17 2017-10-24 西北大学 Rhodol analog derivatives and its preparation method and application
CN109126726A (en) * 2018-09-29 2019-01-04 江苏齐耀生物科技有限公司 A kind of mesoporous magnetic particle preparation method
CN109439314A (en) * 2018-12-07 2019-03-08 武汉工程大学 The preparation method of the magnetic Nano fluorescence probe of specific recognition Fe (III)
CN109439314B (en) * 2018-12-07 2022-05-10 武汉工程大学 Preparation method of magnetic nano fluorescent probe for specifically recognizing Fe (III)
CN110231316A (en) * 2019-04-26 2019-09-13 山西医科大学 The preparation of bimodal nano-probe and its label and imaging to mescenchymal stem cell
CN110231316B (en) * 2019-04-26 2022-01-21 山西医科大学 Preparation of bimodal nanoprobe and labeling and imaging of mesenchymal stem cells by bimodal nanoprobe
CN110961071A (en) * 2019-12-20 2020-04-07 湖北海汇化工科技有限公司 Wastewater treatment agent, preparation method and application thereof, and wastewater treatment method
CN110961071B (en) * 2019-12-20 2022-05-27 湖北海汇化工科技有限公司 Wastewater treatment agent, preparation method and application thereof, and wastewater treatment method
CN115475597A (en) * 2022-08-10 2022-12-16 中国地质大学（武汉） Core-shell magnetic mesoporous silica material, method for preparing same by using iron tailings and application of core-shell magnetic mesoporous silica material
CN115475597B (en) * 2022-08-10 2024-03-29 中国地质大学（武汉） Core-shell magnetic mesoporous silica material, method for preparing material by using iron tailings and application of material

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