CN109439314A - The preparation method of the magnetic Nano fluorescence probe of specific recognition Fe (III) - Google Patents
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Abstract
The present invention relates to a kind of specific recognition Fe3+Magnetic Nano fluorescence probe preparation method, mainly solve that the recycling separation of existing metal ion probe is difficult, easily causes the problems such as pollution.Successively with 3- aminopropyl triethoxysilane, glyoxal, rhodamine hydrazides to the Fe of coated with silica in preparation process3O4Nanoparticle is modified, and having finally obtained being capable of specific recognition Fe3+Magnetic Nano fluorescence probe, and can be recycled easily and fast using Magneto separate.
Description
Technical field
The present invention relates to fluorescence probe and metal ion detection technical fields, and in particular to a kind of specific recognition Fe3+'s
Magnetic Nano fluorescence probe and preparation method thereof.
Background technique
It the detection of heavy metal ion and administers in the most serious in the past few decades to face in always field of environment protection
One of problem.Different types of metal ion can cause different degrees of influence to environmental and biological materials, highly concentrated in organism
Heavy metal ion and the transition element ion accumulation of degree will affect the normal function of cell, generally as the raising of accumulated concentrations is endangered
Evil is also bigger, and the heavy metal pollution in natural water also can carry out potential threat to the health care belt of human body.
Fe3+(or Fe (III)) is one of element most basic in biosystem, to the normal of the maintenance various functions of organism
Operating is of great significance, for example iron ion plays key player during hemoglobin transports oxygen, cell metabolism etc.,
When in human body iron concentration not in normal level when can cause the diseases such as anaemia, heart rate failure, senile dementia.Just because of iron from
Tremendous influence of the son to organism and environment, qualitative and quantitative analysis detection is carried out to it seems particularly necessary.It is usually used at present
The method of iron ion detection includes atomic absorption spectrography (AAS), colorimetric method etc., although these methods can detect iron ion,
But the disadvantages of that there are detection cycles is long, specific selectivity is poor, equipment complex valuableness, it is therefore necessary to it is fast to design new method
Fast sensitive detection iron ion, to meet a large amount of detection need of the field faces such as current environmental protection, biological medicine, analysis science
It asks.Iron ion probe is a kind of excellent solution, has attracted the sight of many scholars in recent years.
Rhodamine B and its derivative are that the artificial synthesized dyestuff of one kind is commonly used for closing with excellent optical property
At metal ion probe.The field achieves many achievements at present, and Goswami is using rhodamine 6G and cigarette hydrazine as Material synthesis
A kind of fluorescence probe, the probe and Fe in acetonitrile/water system3+It can become pink from colourless in conjunction with rear system color, pass through
The variation of color can qualitative detection Fe3+Presence, have very high sensitivity and selectivity.Similar probe further includes
A kind of rhodamine hydrazide derivatives class compound disclosed in CN106146526A, however the generally existing recycling of this kind of probe it is difficult with
And the problem of secondary pollution.
Summary of the invention
It is an object of the invention to solve the above problem of the existing technology, a kind of specific recognition Fe is provided3+Magnetic
Property namo fluorescence probe and preparation method thereof.By the way that rhodamine hydrazides is coupled to Fe3O4Nanoparticle surface obtains magnetism and receives
Rice fluorescence probe, to Fe in water-acetonitrile mixed system3+Specific recognition capability is shown, in addition to macroscopic face
Also there is outside color change good fluorescence response signal, can be carried out point by the way that magnet is simple and quick after the completion of fluorescence probe use
From recycling is convenient not to will cause secondary pollution.To achieve the above object, the technical solution adopted in the present invention is as follows:
(a) magnetic nano-particle of coated with silica is dispersed in alcoholic solvent, adds silane coupling agent and ammonium hydroxide,
Product A is obtained after the reaction was completed；
(b) product A is dispersed in alcoholic solvent, adds aldehyde reagent and acid reagent back flow reaction, obtain product B；
(c) product B is dispersed in alcoholic solvent, adds rhodamine hydrazides and acid reagent back flow reaction, obtain target production
Object --- it being capable of specific recognition Fe3+Magnetic Nano fluorescence probe.
Further, the magnetic nano-particle is specially Fe3O4, the alcoholic solvent is specially ethyl alcohol, described silane coupled
Agent is specially 3- aminopropyl triethoxysilane, and the aldehyde reagent is specially glyoxal, and the acid reagent is specially acetic acid.
Further, the magnetic nano-particle concentration of coated with silica is 1-5g/L in step (a) reaction solution, and silane is even
Join agent, the dosage of ammonium hydroxide is respectively equivalent to (0.5-2.0) % and (0.5-5) % of reaction solution volume.
Further, it is also added into water in step (a), the volume ratio of water and alcoholic solvent is 1:4.
Further, the concentration of product A is 1-5g/L in step (b) reaction solution, and the mass ratio of aldehyde reagent and product A is
10-30:1。
Further, the concentration of product B is 1-5g/L, the quality of rhodamine hydrazides and product B in step (c) reaction solution
Than for 1-15:1.
Further, step (a)-(c) reaction time is 8-16h, is kept stirring during reaction, products therefrom centrifugation point
Repeatedly from rear washing, solvent used in washing is selected from least one of water, alcoholic solvent.
Compared with prior art, the beneficial effects of the present invention are embodied in following aspect: by traditional rhodamine metal ion
Probe conjugate solves the problems, such as that probe recycling is difficult, easily causes secondary pollution in magnetic nano-particle surface；Magnetism obtained
Namo fluorescence probe is in water-acetonitrile system to Fe3+Specific recognition capability is shown, is not done substantially by other metal ions
It disturbs；The modification method of metal probe is relatively simple, low in cost, it is easy to accomplish.
Detailed description of the invention
Fig. 1 is the infrared spectrum comparison diagram of raw material, intermediate product and final product in the embodiment of the present invention 1；
Fig. 2 is ultraviolet suction of the magnetic Nano fluorescence probe in different metal ions solution made from the embodiment of the present invention 2
Receive spectrogram；
Fig. 3 is fluorescence light of the magnetic Nano fluorescence probe in different metal ions solution made from the embodiment of the present invention 3
Spectrogram.
Specific embodiment
To make those of ordinary skill in the art fully understand technical solution of the present invention and beneficial effect, below in conjunction with specific
Embodiment is further described.
Rhodamine hydrazide structure used in various embodiments of the present invention is as follows:
The magnetic nano-particle of coated with silica is the preparation method is as follows: by Fe3O4Magnetic nano-particle is dispersed in ethanol water
In solution, ammonium hydroxide mechanical stirring in a sealed meter environment is added, tetraethyl orthosilicate is during which slowly added dropwise, is stirred to react at room temperature
8-16h is attracted with magnet and is settled, washing separation.
Embodiment 1
By the Fe of coated with silica3O4Nanoparticle is dispersed in 100mL water-alcohol in the mixed solvent (VEthyl alcohol: VWater=4:1),
Obtain the dispersion liquid A that concentration is 2.5g/L.1mL 3- aminopropyl triethoxysilane, 2.5mL ammonium hydroxide are added, is stirred at room temperature
It is centrifugated after mixing reaction 12h, products therefrom water and ethyl alcohol alternately washing 3 times, the as Fe of surface modification amino3O4Nanometer
Particle.
By the Fe of surface modification amino3O4Nanoparticle is dispersed in 40mL ethyl alcohol, and obtaining concentration is 2.5g/L dispersion liquid
B.2.0g glyoxal (40%, volume fraction, similarly hereinafter) and 2 drop glacial acetic acid are added, is centrifugated after being stirred at reflux reaction 10h,
Products therefrom ethanol washing 3 times, the as Fe of surface modification aldehyde radical3O4Nanoparticle.
By the Fe of surface modification aldehyde radical3O4Nanoparticle is dispersed in 40mL ethyl alcohol, obtains the dispersion that concentration is 2.5g/L
Liquid C.0.75g rhodamine hydrazides and 2 drop glacial acetic acid are added, is centrifugated after being stirred at reflux reaction 10h, products therefrom ethyl alcohol
Washing, as target product --- magnetic Nano fluorescence probe.
The intermediate product that the first step is obtained respectively --- the Fe of surface modification amino3O4Nanoparticle (a), raw material Luo Dan
Bright hydrazides (b) and magnetic Nano probe (c) have carried out infrared spectrum analysis, as a result as shown in Figure 1.1090cm in Fig. 1-a-1Place
For the antisymmetric stretching vibration peak of Si-O-Si, 1380cm-1Place is methyl flexural vibrations peak, 590cm-1Place is Fe-O-Fe key
Characteristic absorption peak, this shows that silane coupling agent successfully modifies the Fe for having arrived coated with silica3O4Nanoparticle surface.Figure
2970cm in 1-b-1And 2987cm-1Place is C-H stretching vibration peak, 1700-500cm-1A series of absorption peaks in range belong to
The structures such as the phenyl ring in rhodamine hydrazide structure；Wherein 1724cm-1The strong peak that place occurs is C=O stretching vibration absworption peak.Fig. 1-
In 1587cm in c-1Locating emerging absorption peak is C=N stretching vibration absworption peak.In summary, rhodamine hydrazides passes through second two
Aldehyde has been coupled to Fe3O4@SiO2Surface.
Embodiment 2
By the Fe of coated with silica3O4Nanoparticle is dispersed in 100mL water-alcohol in the mixed solvent (VEthyl alcohol: VWater=4:1),
Obtain the dispersion liquid A that concentration is 5g/L.2mL 3- aminopropyl triethoxysilane, 5mL ammonium hydroxide are added, stirring is anti-at room temperature
It is centrifugated after answering 12h, products therefrom water and ethyl alcohol alternately washing 3 times, the as Fe of surface modification amino3O4Nanoparticle
Son.
By the Fe of surface modification amino3O4Nanoparticle is dispersed in 40mL ethyl alcohol, and obtaining concentration is 5g/L dispersion liquid B.
6g glyoxal (40%) and 2 drop glacial acetic acid are added, is centrifugated after being stirred at reflux reaction 10h, products therefrom ethanol washing 3
It is secondary, the as Fe of surface modification aldehyde radical3O4Nanoparticle.
By the Fe of surface modification aldehyde radical3O4Nanoparticle is dispersed in 40mL ethyl alcohol, obtains the dispersion liquid that concentration is 5g/L
C.3g rhodamine hydrazides and 2 drop glacial acetic acid are added, is centrifugated after being stirred at reflux reaction 10h, products therefrom ethanol washing,
As target product --- magnetic Nano fluorescence probe.
Using volume ratio for 1:1 acetonitrile-water mixed liquor as solvent, prepare (100 μM of scope of experiment of same concentrations respectively
Within) BaCl2、CaCl2、CuCl2、FeCl3、HgCl2、KCl、FeCl2、NaCl、MgCl2Then metal ion solution respectively adds
Enter magnetic Nano fluorescence probe made from 10mg, sampling carries out ultraviolet absorption spectroscopy after standing 15min, as a result such as Fig. 2 institute
Show.The color that period is observed visually ferric ion solutions is gradually converted into bright-coloured pink, and other metal ion solutions do not have
Occur any color change.Ultra-violet absorption spectrum shown in Fig. 2 has further confirmed above-mentioned phenomenon, Na+、K+、Mg2+、Ba2+、
Ca2+、Cu2+、 Hg2+、Fe2+Without apparent absorption peak in solion spectrogram, and Fe3+Solution has apparent suction at 560nm
Peak is received, this illustrates the magnetic Nano fluorescence probe really to Fe3+With specific recognition capability.Probe can be completed with magnet
Absorption and recycling, are cleaned spare.
Embodiment 3
By the Fe of coated with silica3O4Nanoparticle is dispersed in 100mL water-alcohol in the mixed solvent (VEthyl alcohol: VWater=4:1),
Obtain the dispersion liquid A that concentration is 1g/L.0.5mL 3- aminopropyl triethoxysilane, 0.5mL ammonium hydroxide are added, is stirred at room temperature
It is centrifugated after mixing reaction 12h, products therefrom water and ethyl alcohol alternately washing 3 times, the as Fe of surface modification amino3O4Nanometer
Particle.
By the Fe of surface modification amino3O4Nanoparticle is dispersed in 40mL ethyl alcohol, and obtaining concentration is 1g/L dispersion liquid B.
0.4g glyoxal (40%) and 2 drop glacial acetic acid are added, is centrifugated after being stirred at reflux reaction 10h, products therefrom is washed with ethyl alcohol
Wash 3 times, the as Fe of surface modification aldehyde radical3O4Nanoparticle.
By the Fe of surface modification aldehyde radical3O4Nanoparticle is dispersed in 40mL ethyl alcohol, obtains the dispersion liquid that concentration is 1g/L
C.0.04g rhodamine hydrazides and 2 drop glacial acetic acid are added, is centrifugated after being stirred at reflux reaction 10h, products therefrom is washed with ethyl alcohol
Wash, as target product --- magnetic Nano fluorescence probe.
BaCl is prepared respectively according to the method for embodiment 22、CaCl2、CuCl2、FeCl3、HgCl2、KCl、 FeCl2、NaCl、
MgCl2Then magnetic Nano fluorescence probe made from 10mg is respectively added in metal ion solution, sampling progress is glimmering after standing 15min
Light spectrum analysis, as a result as shown in Figure 3.Fig. 3 shows Na+、 K+、Mg2+、Ba2+、Ca2+、Cu2+、Hg2+、Fe2+Metal ion solution
There is no apparent fluorescence signal to change, and Fe3+Solution has very strong fluorescence intensity at 586nm, this result further confirms
According to magnetic Nano probe made from the method for the present invention specific it can must identify Fe3+, and probe and Fe3+Product is complexed
Show stronger fluorescence signal.
Embodiment 4
By the Fe of coated with silica3O4Nanoparticle is dispersed in 100mL water-alcohol in the mixed solvent (VEthyl alcohol: VWater=4:1),
Obtain the dispersion liquid A that concentration is 1g/L.0.5mL 3- aminopropyl triethoxysilane, 0.5mL ammonium hydroxide are added, is stirred at room temperature
It is centrifugated after mixing reaction 12h, products therefrom water and ethyl alcohol alternately washing 3 times, the as Fe of surface modification amino3O4Nanometer
Particle.
By the Fe of surface modification amino3O4Nanoparticle is dispersed in 40mL ethyl alcohol, and obtaining concentration is 1g/L dispersion liquid B.
2g glyoxal (40%) and 2 drop glacial acetic acid are added, is centrifugated after being stirred at reflux reaction 10h, products therefrom ethanol washing 3
It is secondary, the as Fe of surface modification aldehyde radical3O4Nanoparticle.
By the Fe of surface modification aldehyde radical3O4Nanoparticle is dispersed in 40mL ethyl alcohol, obtains the dispersion liquid that concentration is 1g/L
C.0.75g rhodamine hydrazides and 2 drop glacial acetic acid are added, is centrifugated after being stirred at reflux reaction 10h, products therefrom is washed with ethyl alcohol
Wash, as target product --- magnetic Nano fluorescence probe.
Embodiment 5
By the Fe of coated with silica3O4Nanoparticle is dispersed in 100mL water-alcohol in the mixed solvent (VEthyl alcohol: VWater=4:1),
Obtain the dispersion liquid A that concentration is 2.5g/L.1mL 3- aminopropyl triethoxysilane, 2.5mL ammonium hydroxide are added, is stirred at room temperature
It is centrifugated after mixing reaction 12h, products therefrom water and ethyl alcohol alternately washing 3 times, the as Fe of surface modification amino3O4Nanometer
Particle.
By the Fe of surface modification amino3O4Nanoparticle is dispersed in 40mL ethyl alcohol, and obtaining concentration is 2.5g/L dispersion liquid
B.6g glyoxal (40%) and 2 drop glacial acetic acid are added, is centrifugated after being stirred at reflux reaction 10h, products therefrom is washed with ethyl alcohol
Wash 3 times, the as Fe of surface modification aldehyde radical3O4Nanoparticle.
By the Fe of surface modification aldehyde radical3O4Nanoparticle is dispersed in 40mL ethyl alcohol, obtains the dispersion that concentration is 2.5g/L
Liquid C.3g rhodamine hydrazides and 2 drop glacial acetic acid are added, is centrifugated after being stirred at reflux reaction 10h, products therefrom is washed with ethyl alcohol
Wash, as target product --- magnetic Nano fluorescence probe.
Embodiment 6
By the Fe of coated with silica3O4Nanoparticle is dispersed in 100mL water-alcohol in the mixed solvent (VEthyl alcohol: VWater=4:1),
Obtain the dispersion liquid A that concentration is 2.5g/L.1mL 3- aminopropyl triethoxysilane, 2.5mL ammonium hydroxide are added, is stirred at room temperature
It is centrifugated after mixing reaction 12h, products therefrom water and ethyl alcohol alternately washing 3 times, the as Fe of surface modification amino3O4Nanometer
Particle.
By the Fe of surface modification amino3O4Nanoparticle is dispersed in 40mL ethyl alcohol, and obtaining concentration is 2.5g/L dispersion liquid
B.0.4g glyoxal (40%) and 2 drop glacial acetic acid are added, is centrifugated after being stirred at reflux reaction 10h, products therefrom ethyl alcohol
Washing 3 times, the as Fe of surface modification aldehyde radical3O4Nanoparticle.
By the Fe of surface modification aldehyde radical3O4Nanoparticle is dispersed in 40mL ethyl alcohol, obtains the dispersion that concentration is 2.5g/L
Liquid C.0.1g rhodamine hydrazides and 2 drop glacial acetic acid are added, is centrifugated after being stirred at reflux reaction 10h, products therefrom ethyl alcohol
Washing, as target product --- magnetic Nano fluorescence probe.
Embodiment 7
By the Fe of coated with silica3O4Nanoparticle is dispersed in 100mL water-alcohol in the mixed solvent (VEthyl alcohol: VWater=4:1),
Obtain the dispersion liquid A that concentration is 5g/L.2mL 3- aminopropyl triethoxysilane, 5mL ammonium hydroxide are added, stirring is anti-at room temperature
It is centrifugated after answering 12h, products therefrom water and ethyl alcohol alternately washing 3 times, the as Fe of surface modification amino3O4Nanoparticle
Son.
By the Fe of surface modification amino3O4Nanoparticle is dispersed in 40mL ethyl alcohol, and obtaining concentration is 5g/L dispersion liquid B.
0.4g glyoxal (40%) and 2 drop glacial acetic acid are added, is centrifugated after being stirred at reflux reaction 10h, products therefrom is washed with ethyl alcohol
Wash 3 times, the as Fe of surface modification aldehyde radical3O4Nanoparticle.
By the Fe of surface modification aldehyde radical3O4Nanoparticle is dispersed in 40mL ethyl alcohol, obtains the dispersion liquid that concentration is 5g/L
C.0.1g rhodamine hydrazides and 2 drop glacial acetic acid are added, is centrifugated after being stirred at reflux reaction 10h, products therefrom is washed with ethyl alcohol
Wash, as target product --- magnetic Nano fluorescence probe.
Embodiment 8
By the Fe of coated with silica3O4Nanoparticle is dispersed in 100mL water-alcohol in the mixed solvent (VEthyl alcohol: VWater=4:1),
Obtain the dispersion liquid A that concentration is 5g/L.2mL 3- aminopropyl triethoxysilane, 5mL ammonium hydroxide are added, stirring is anti-at room temperature
It is centrifugated after answering 12h, products therefrom water and ethyl alcohol alternately washing 3 times, the as Fe of surface modification amino3O4Nanoparticle
Son.
By the Fe of surface modification amino3O4Nanoparticle is dispersed in 40mL ethyl alcohol, and obtaining concentration is 5g/L dispersion liquid B.
2g glyoxal (40%) and 2 drop glacial acetic acid are added, is centrifugated after being stirred at reflux reaction 10h, products therefrom ethanol washing 3
It is secondary, the as Fe of surface modification aldehyde radical3O4Nanoparticle.
By the Fe of surface modification aldehyde radical3O4Nanoparticle is dispersed in 40mL ethyl alcohol, obtains the dispersion liquid that concentration is 5g/L
C.0.75g rhodamine hydrazides and 2 drop glacial acetic acid are added, is centrifugated after being stirred at reflux reaction 10h, products therefrom is washed with ethyl alcohol
Wash, as target product --- magnetic Nano fluorescence probe.
Claims (8)
1. a kind of preparation method of the magnetic Nano fluorescence probe of specific recognition Fe (III), which is characterized in that including following step
It is rapid:
(a) magnetic nano-particle of coated with silica is dispersed in alcoholic solvent, adds silane coupling agent and ammonium hydroxide, reacted
Product A is obtained after the completion；
(b) product A is dispersed in alcoholic solvent, adds aldehyde reagent and acid reagent back flow reaction, obtain product B；
(c) product B is dispersed in alcoholic solvent, adds rhodamine hydrazides and acid reagent back flow reaction, be separated by solid-liquid separation, washing is
It can.
2. preparation method as described in claim 1, it is characterised in that: the magnetic nano-particle is specially Fe3O4, the alcohol
Solvent is specially ethyl alcohol, and the silane coupling agent is specially 3- aminopropyl triethoxysilane, and the aldehyde reagent is specially second two
Aldehyde, the acid reagent are specially acetic acid.
3. preparation method as described in claim 1, it is characterised in that: the magnetism of coated with silica in step (a) reaction solution
Nanoparticle concentration is 1-5g/L, silane coupling agent, ammonium hydroxide dosage be respectively equivalent to reaction solution volume (0.5-2.0) % and
(0.5-5) %.
4. preparation method as described in claim 1, it is characterised in that: be also added into water, the body of water and alcoholic solvent in step (a)
Product is than being 1:4.
5. preparation method as described in claim 1, it is characterised in that: the concentration of product A is 1-5g/ in step (b) reaction solution
The mass ratio of L, aldehyde reagent and product A are 10-30:1.
6. preparation method as described in claim 1, it is characterised in that: the concentration of product B is 1-5g/ in step (c) reaction solution
The mass ratio of L, rhodamine hydrazides and product B are 1-15:1.
7. preparation method as described in claim 1, it is characterised in that: step (a)-(c) reaction time is 8-16h, reaction
Period keeps stirring, products therefrom centrifuge separation after wash repeatedly, wash used in solvent in water, alcoholic solvent at least
It is a kind of.
8. according to the magnetic Nano fluorescence probe of specific recognition Fe (III) made from any one method of claim 1-7.
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| CN111899955A (en) * | 2020-09-17 | 2020-11-06 | 青岛大学 | Magnetic probe material, magnetic probe, preparation method and application of magnetic probe and molecular marker |
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| CN111899955B (en) * | 2020-09-17 | 2024-01-23 | 青岛大学 | Magnetic probe material, magnetic probe, preparation method and application thereof and molecular marker |
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