CN105067577A - Dual emission rate type fluorescent probe for visually detecting carbon dots-Au nanoclusters of mercury ions and preparation method - Google Patents
Dual emission rate type fluorescent probe for visually detecting carbon dots-Au nanoclusters of mercury ions and preparation method Download PDFInfo
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Abstract
The invention relates to a dual emission rate type fluorescent probe for visually detecting carbon dots-Au nanoclusters of mercury ions and a preparation method. Dual-emission composite silicon dioxide nanoparticles are composite silicon dioxide nanoparticles formed by utilizing carbon dot covered silicon dioxide particles as cores and covalently coupling the surfaces of the carbon dot covered silicon dioxide particles with the Au nanoclusters after surface amination. The carbon dots located in the silicon dioxide nanoparticle cores are taken as reference fluorescence signals, the Au nanoclusters on the outer layers are taken as response fluorescence signals, and the signals are used for Hg<2+> selective recognition. The Au nanoclusters as the response fluorescence signals are connected to the surface of a silicon layer through covalent bond connection, and one stable nano-fluorescent probe is formed. When the dual-fluorescence composite nanoparticles are taken as the rate type fluorescent probes, the intensity of the carbon dot fluorescence signals in the cores basically keep unchanged, and the Au nanoclusters on the outer layers can be bonded with Hg<2+> selectively so as to result in fluorescence quenching of the Au nanoclusters on the outer layers.
Description
Technical field
The present invention relates to a kind of fluorescence probe and preparation method thereof, fluorescence probe and preparation method thereof is detected, specifically a kind of fluorescence probe based on the two emitting fluorescence input mercury ion of carbon point-gold nano cluster and preparation method thereof in particular to a kind of visual analyzing for heavy metal ion mercury ion.
Background technology
The pollution of heavy metal ion is a very serious environment and ecological problem all the time.Especially with mercury ion (Hg
2+) for the pollutant of representative is once after entered environment, can not fast decoupled, but extended residual is in soil, water, air, produces unfailing pollution.The health of mercury ion to human body entering human body also also exists significant damage, and e.g., mercury ion has serious damage capability to the nervous system of people, hemopoietic system, respiratory system and kidney etc.Therefore, a kind of easy, Hg fast and efficiently of exploitation
2+assay technology is very necessary.In recent years, the instrument analysis technologies such as atomic absorption spectrum, X-ray spectrum, the resonance of induced-coupled plasma mass spectrum electronics superparamagnetic have been widely used in the detection of heavy metal ion, but these technology are very consuming time, and testing expense is high, and need to carry out complicated pre-treatment to sample.
Fluorometry due to highly sensitive, selectivity good, the feature such as simple and efficient to handle and have obvious detection advantage, obtains extensive concern in the field such as environmental monitoring and food security.In recent years, to be designed based on the fluorescence probe of Prof. Du Yucang organic dyestuff and for Hg
2+detect, but this type of probe existence synthesis and modification complexity, the problems such as quantum yield is low, and water-soluble and light stability is poor, limit their practical application.The mercury ion fluorescence probe of previous report generally adopts single fluorescent quenching pattern, and the factor impacts such as the easy examined substrate concentration of measurement result, external environment condition and instrument condition change, cause data distortion, thus reduce the accuracy of measurement result.For above-mentioned existing problems, the present invention aims to provide a kind of ratio fluorescent method for detecting mercury ion.
Ratio fluorescent method is the fluorescence intensity by measuring two different wave length places, with its ratio for signal parameter measures the analytical approach of object.Compare the conventional fluorescent probe based on single fluorescence signal, it can reduce or eliminate the data distortion that the factors such as detection substrate concentration, external environment condition and instrument condition change cause, and improves the accuracy of measurement result.Meanwhile, the change of two kinds of emitting at different wavelengths light intensities can cause the change of detection system color, and testing process more reliably, is easily differentiated.
The present invention aims to provide two emission ratios type mercury ion fluorescence probe of a kind of carbon point-gold nano cluster for mercury ion quick visualization detection in authentic sample and preparation method thereof.
Summary of the invention
The object of the present invention is to provide a kind of two emission ratios type fluorescence probes for Visual retrieval mercury ion and preparation method thereof.
Of the present invention pair of emission ratios type fluorescence probe, is made up of two transmitting composite silicon dioxide nano particle.Described two composite silicon dioxide nano particles of launching are with the composite silicon dioxide nano particle that the silicon dioxide granule of carbon coated point is kernel, covalent coupling gold nano cluster is formed after its surface amination.In the structure shown here, be positioned at the carbon point of Nano particles of silicon dioxide core inside as reference fluorescent signal, and outer field gold nano cluster responsively fluorescence signal, for Hg
2+selective recognition.Wherein, carbon point, as reference signal, because it is embedded in core, effectively can avoid leakage problem, because herein is provided a reliable reference signal; And responsively the gold nano cluster of fluorescence signal is connected to the surface of silicon layer by the mode that covalent bond connects, define a stable namo fluorescence probe.When this pair of fluorescent composite nanoparticle is as Ratiometric fluorescent probe, the carbon point fluorescence signal intensity in core remains unchanged substantially, and outer field gold nano cluster can optionally with Hg
2+in conjunction with, thus cause the fluorescent quenching of outer gold nano cluster.This composite nanoparticle can develop into Hg
2+the Ratiometric fluorescent probe that content quantitative measures.
The preparation method of two emission ratios type fluorescence probes of the present invention, step is as follows:
(1) the amination fluorescent silicon dioxide nano particle of carbon coated point is prepared
After being stirred by the mixed solution of cyclohexane, triton x-100, n-hexyl alcohol and water, add ethyl orthosilicate wherein, after stirring, add functional polyorganosiloxane carbon point and ammoniacal liquor wherein; After reaction 18 ~ 24h, add isopropyl alcohol and carry out breakdown of emulsion, centrifugal alcohol wash, until centrifuged supernatant till fluorescence spectrophotometer detects unstressed configuration signal, obtain the fluorescent silicon dioxide nano particle of carbon coated point, by its ultrasonic disperse in absolute ethyl alcohol; Add 3-aminopropyl triethoxysilane, be heated with stirring to backflow, the upper end drying tube sealing that drying agent is housed of reflux, after reaction 12 ~ 24h, centrifuging product, obtains the pressed powder of the amination Nano particles of silicon dioxide of carbon coated point;
(2) structure of two transmitting composite silicon dioxide nano particle
The pressed powder of the amination Nano particles of silicon dioxide of carbon coated point is scattered in phosphate buffer; 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide and N-hydroxy-succinamide solution is added in gold nano cluster solution, stirred at ambient temperature 0.5 ~ 1h, adds the phosphate buffer of the amination Nano particles of silicon dioxide of carbon coated point wherein; After reaction 12-24h, centrifuging product, obtains two transmitting composite silicon dioxide nano particle, and is dispersed in ultrapure water;
(3) two transmitting composite silicon dioxide nano particle detects mercury ion
Standard solution containing mercury ion and solution to be measured being joined the two of step (2) gained launches in the aqueous solution of composite silicon dioxide nano particle, fluorescence spectrophotometer is utilized to measure fluorescence emission spectrum, record the fluorescence photo that lower pair of different mercury ion content launches composite silicon dioxide nano particle, and according to the fluorescence intensity of two emission peak than Criterion curve, contrast standard curve obtains the concentration of mercury ion in solution to be measured.
In step (1), the volume ratio of described cyclohexane, triton x-100, n-hexyl alcohol, water, ethyl orthosilicate, carbon quantum dot and ammoniacal liquor is preferably 152:35.4:35.4:7.6:1:0.5:4; The fluorescent silicon dioxide nano particle of every milligram of carbon coated point need add 3-10 μ L3-aminopropyl triethoxysilane.
In step (2), the concentration of described 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide is 50 ~ 100mmol/L, the concentration of N-hydroxy-succinamide solution is that the mol ratio of 100 ~ 500mmol/L, 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide and N-hydroxy-succinamide is preferably 1:4.
In step (2), the pH value of described phosphate buffer is 6.5 ~ 7.0, and the concentration of phosphate buffer is 10 ~ 50mmol/L.
The maximum emission wavelength of carbon point is 350-550nm.
The maximum emission wavelength of gold nano cluster is 580-670nm.
Advantage of the present invention and good effect: the present invention can launch the composite particle Ratiometric fluorescent probe of two fluorescence under constructing single excitation wavelength.Specifically invent two emission ratios type mercury ion fluorescence probe of a kind of carbon point-gold nano cluster for mercury ion quick visualization detection in authentic sample and preparation method thereof.Preparation fluorescence probe can be used in Visual retrieval mercury ion, can Visual retrieval to 6.35 μm of ol/L mercury ion residue.
Accompanying drawing explanation
Fig. 1 is carbon point (a), gold nano cluster (b) and two fluorescence spectrum figure (excitation wavelength is 380nm) launching composite silicon dioxide nano particle (c).
Fig. 2 is two transmitting composite silicon dioxide nano particle shape appearance figure of the present invention.
Fig. 3 is that two composite silicon dioxide nano particle of launching is to variable concentrations Hg
2+fluorescence response curve.In figure, 460nm is the fluorescence emission peak of carbon point, and 650nm is the fluorescence emission peak of gold nanoclusters.Show in figure: along with the increase of mercury ion content, carbon point remains unchanged substantially in the fluorescence intensity of 460nm, and gold nanoclusters red fluorescence intensity (650nm) reduces gradually; To be presented as and gold nanoclusters reduces gradually in the fluorescence intensity of 650nm from figure.
Fig. 4 is the fluorescence photos of two transmitting composite silicon dioxide nano particles of the present invention under variable concentrations mercury ion exists.As seen from the figure, along with the increase of mercury ion content, the fluorescence color of the solution of two transmitting composite silicon dioxide nano particle gradually becomes blue by redness, can realize Visual retrieval, can Visual retrieval to 6.35 μm of ol/L mercury ion residue.
Embodiment
Embodiment 1
(1) the amination fluorescent silicon dioxide nano particle of carbon coated point is prepared
Adopt the method for openly Chinese patent (publication number: CN103421495A), obtained functional polyorganosiloxane carbon point; Do not limit other preparation method.
This experiment prepares the Nano particles of silicon dioxide of carbon coated point by reverse micro emulsion method.Specific experiment step is as follows: in 25mL round-bottomed flask, add 7.7mL cyclohexane, 1.77mL triton x-100 and 1.77mL n-hexyl alcohol respectively, add 380 μ L water subsequently, this system vigorous stirring is about 10min, to form the Reverse Microemulsion System of stable and uniform; After Reverse Microemulsion System is formed, in flask, add 50 μ L ethyl orthosilicates, add 25 μ L brand-new carbon quantum dot and 200 μ L ammoniacal liquor (25wt%) after stirring wherein, reaction system is placed in room temperature reaction; After reaction 18h, the isopropyl alcohol adding three times of reactant liquor volumes in reaction system carries out breakdown of emulsion, obtains flocculent deposit.By centrifugal for reactant liquor alcohol wash, 5 times repeatedly, until centrifuged supernatant till fluorescence spectrophotometer detects unstressed configuration signal, obtain the fluorescent silicon dioxide nano particle of carbon coated point, get 5mg ultrasonic disperse in 20mL absolute ethyl alcohol; Add 50 μ L3-aminopropyl triethoxysilanes, be heated with stirring to backflow, the upper end drying tube sealing that drying agent is housed of reflux, after reaction 24h, centrifuging product, obtains the pressed powder of the amination Nano particles of silicon dioxide of carbon coated point.
(2) gold nano cluster is prepared
Adopt the method for openly Chinese patent (Authorization Notice No.: CN102866139B), the aqueous solution of obtained gold nano cluster; Do not limit other preparation method.
(3) structure of two transmitting composite silicon dioxide nano particle
The pressed powder getting the amination Nano particles of silicon dioxide of 5mg carbon coated point is scattered in 10mL10mMpH7.0 phosphate buffer; Get 0.1mL gold nano cluster solution, 1mL is diluted to 10mMpH7.0 phosphate buffer, add 0.5mL100mM1-(3-dimethylamino-propyl)-3-ethyl carbodiimide and 0.4mL500mMN-N-Hydroxysuccinimide solution wherein, stirred at ambient temperature 0.5h; Add the phosphate buffer of the amination Nano particles of silicon dioxide of 1mL carbon coated point wherein, at being placed in 4 DEG C, stir 12h; After reaction terminates, centrifuging product, is scattered in 5mL ultrapure water.Fluorescence emission spectrum and the pattern of two transmitting composite silicon dioxide nano particle are shown in Fig. 1 and Fig. 2.
(4) two transmitting composite silicon dioxide nano particle detects mercury ion
In the aqueous solution of two transmitting composite silicon dioxide nano particle, add concentration is respectively the mercury ion standard solution of 0 ~ 40 μM and solution to be measured, measures system fluorescence emission spectrum, the results are shown in Figure 3 after mixing rear room temperature reaction 10min.Carbon point remains unchanged substantially in the fluorescence intensity of 460nm, and gold nanoclusters red fluorescence intensity (650nm) reduces gradually; To be presented as and gold nanoclusters reduces gradually in the fluorescence intensity of 650nm from figure.Can be found out by fluorescence photo, along with the increase of mercury ion content, the fluorescence of the solution of two transmitting composite silicon dioxide nano particle gradually becomes blue by the redness become clear, and fluorescence color change procedure is obvious, can realize Visual retrieval.
Embodiment 2
(1) the amination fluorescent silicon dioxide nano particle of carbon coated point is prepared
Adopt the method for openly Chinese patent (publication number: CN103421495A), obtained functional polyorganosiloxane carbon point.
This experiment prepares the Nano particles of silicon dioxide of carbon coated point by reverse micro emulsion method.Specific experiment step is as follows: in 25mL round-bottomed flask, add 7.7mL cyclohexane, 1.77mL triton x-100 and 1.77mL n-hexyl alcohol respectively, add 380 μ L water subsequently, this system vigorous stirring is about 10min, to form the Reverse Microemulsion System of stable and uniform; After Reverse Microemulsion System is formed, in flask, add 50 μ L ethyl orthosilicates, add 25 μ L brand-new carbon quantum dot and 200 μ L ammoniacal liquor (25wt%) after stirring wherein, reaction system is placed in room temperature reaction; After reaction 20h, the isopropyl alcohol adding three times of reactant liquor volumes in reaction system carries out breakdown of emulsion, obtains flocculent deposit.By centrifugal for reactant liquor alcohol wash, 5 times repeatedly, until centrifuged supernatant till fluorescence spectrophotometer detects unstressed configuration signal, obtain the fluorescent silicon dioxide nano particle of carbon coated point, get 5mg ultrasonic disperse in 20mL absolute ethyl alcohol; Add 15 μ L3-aminopropyl triethoxysilanes, be heated with stirring to backflow, the upper end drying tube sealing that drying agent is housed of reflux, after reaction 12h, centrifuging product, obtains the pressed powder of the amination Nano particles of silicon dioxide of carbon coated point.
(2) gold nano cluster is prepared
Adopt the method for openly Chinese patent (Authorization Notice No.: CN102866139B), the aqueous solution of obtained gold nano cluster.
(3) structure of two transmitting composite silicon dioxide nano particle
The pressed powder getting the amination Nano particles of silicon dioxide of 5mg carbon coated point is scattered in 10mL50mMpH6.5 phosphate buffer; Get 0.1mL gold nano cluster solution, 1mL is diluted to 50mMpH6.5 phosphate buffer, add 1.5mL50mM1-(3-dimethylamino-propyl)-3-ethyl carbodiimide and 1mL300mMN-N-Hydroxysuccinimide solution wherein, stirred at ambient temperature 0.8h; Add the phosphate buffer of the amination Nano particles of silicon dioxide of 1mL carbon coated point wherein, at being placed in 4 DEG C, stir 24h; After reaction terminates, centrifuging product, is scattered in 5mL ultrapure water.Fluorescence emission spectrum and the pattern of two transmitting composite silicon dioxide nano particle are shown in Fig. 1 and Fig. 2.
(4) two transmitting composite silicon dioxide nano particle detects mercury ion
In the aqueous solution of two transmitting composite silicon dioxide nano particle, add concentration is respectively the mercury ion standard solution of 0 ~ 40 μM and solution to be measured, measures system fluorescence emission spectrum, the results are shown in Figure 3 after mixing rear room temperature reaction 10min.Carbon point remains unchanged substantially in the fluorescence intensity of 460nm, and gold nanoclusters red fluorescence intensity (650nm) reduces gradually; To be presented as and gold nanoclusters reduces gradually in the fluorescence intensity of 650nm from figure.Can be found out by fluorescence photo, along with the increase of mercury ion content, the fluorescence of the solution of two transmitting composite silicon dioxide nano particle gradually becomes blue by the redness become clear, and fluorescence color change procedure is obvious, can realize Visual retrieval.
Embodiment 3
(1) the amination fluorescent silicon dioxide nano particle of carbon coated point is prepared
Adopt the method for openly Chinese patent (publication number: CN103421495A), obtained functional polyorganosiloxane carbon point.
This experiment prepares the Nano particles of silicon dioxide of carbon coated point by reverse micro emulsion method.Specific experiment step is as follows: in 25mL round-bottomed flask, add 7.7mL cyclohexane, 1.77mL triton x-100 and 1.77mL n-hexyl alcohol respectively, add 380 μ L water subsequently, this system vigorous stirring is about 10min, to form the Reverse Microemulsion System of stable and uniform; After Reverse Microemulsion System is formed, in flask, add 50 μ L ethyl orthosilicates, add 25 μ L brand-new carbon quantum dot and 200 μ L ammoniacal liquor (25wt%) after stirring wherein, reaction system is placed in room temperature reaction; After reaction 24h, the isopropyl alcohol adding three times of reactant liquor volumes in reaction system carries out breakdown of emulsion, obtains flocculent deposit.By centrifugal for reactant liquor alcohol wash, 5 times repeatedly, until centrifuged supernatant till fluorescence spectrophotometer detects unstressed configuration signal, obtain the fluorescent silicon dioxide nano particle of carbon coated point, get 5mg ultrasonic disperse in 20mL absolute ethyl alcohol; Add 30 μ L3-aminopropyl triethoxysilanes, be heated with stirring to backflow, the upper end drying tube sealing that drying agent is housed of reflux, after reaction 20h, centrifuging product, obtains the pressed powder of the amination Nano particles of silicon dioxide of carbon coated point.
(2) gold nano cluster is prepared
Adopt the method for openly Chinese patent (Authorization Notice No.: CN102866139B), the aqueous solution of obtained gold nano cluster.
(3) structure of two transmitting composite silicon dioxide nano particle
The pressed powder getting the amination Nano particles of silicon dioxide of 5mg carbon coated point is scattered in 10mL10mMpH7.0 phosphate buffer; Get 0.1mL gold nano cluster solution, be diluted to 1mL with 30mMpH7.0 phosphate buffer, add 1mL75mM1-(3-dimethylamino-propyl)-3-ethyl carbodiimide and 3mL100mMN-N-Hydroxysuccinimide solution wherein, stirred at ambient temperature 1h; Add the phosphate buffer of the amination Nano particles of silicon dioxide of 1mL carbon coated point wherein, at being placed in 4 DEG C, stir 18h; After reaction terminates, centrifuging product, is scattered in 5mL ultrapure water.Fluorescence emission spectrum and the pattern of two transmitting composite silicon dioxide nano particle are shown in Fig. 1 and Fig. 2.
(4) two transmitting composite silicon dioxide nano particle detects mercury ion
In the aqueous solution of two transmitting composite silicon dioxide nano particle, add concentration is respectively the mercury ion standard solution of 0 ~ 40 μM and solution to be measured, measures system fluorescence emission spectrum, the results are shown in Figure 3 after mixing rear room temperature reaction 10min.Carbon point remains unchanged substantially in the fluorescence intensity of 460nm, and gold nanoclusters red fluorescence intensity (650nm) reduces gradually; To be presented as and gold nanoclusters reduces gradually in the fluorescence intensity of 650nm from figure.Can be found out by fluorescence photo, along with the increase of mercury ion content, the fluorescence of the solution of two transmitting composite silicon dioxide nano particle gradually becomes blue by the redness become clear, and fluorescence color change procedure is obvious, can realize Visual retrieval.
Open and a kind of two emission ratios type fluorescence probe of carbon point-gold nano cluster of Visual retrieval mercury ion that proposes of the present invention and preparation method, those skilled in the art are by using for reference present disclosure, the links such as suitable feed change and process route realize, although method of the present invention and technology of preparing are described by preferred embodiment, person skilled obviously can change Method and Technology route as herein described or reconfigure not departing from content of the present invention, spirit and scope, realizes final technology of preparing.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the art, they are deemed to be included in spirit of the present invention, scope and content.
Claims (8)
1. the two emission ratios type fluorescence probe of the carbon point-gold nano cluster of a Visual retrieval mercury ion; Be made up of two transmitting composite silicon dioxide nano particle; Two transmitting composite silicon dioxide nano particle is with the composite silicon dioxide nano particle that the silicon dioxide granule of carbon coated point is kernel, covalent coupling gold nano cluster is formed after its surface amination.
2. the preparation method of two emission ratios type fluorescence probes of claim 1, is characterized in that step is as follows:
(1) the amination fluorescent silicon dioxide nano particle of carbon coated point is prepared
After being stirred by the mixed solution of cyclohexane, triton x-100, n-hexyl alcohol and water, add ethyl orthosilicate wherein, after stirring, add functional polyorganosiloxane carbon point and ammoniacal liquor wherein; After reaction 18 ~ 24h, add isopropyl alcohol and carry out breakdown of emulsion, centrifugal alcohol wash, until centrifuged supernatant till fluorescence spectrophotometer detects unstressed configuration signal, obtain the fluorescent silicon dioxide nano particle of carbon coated point, by its ultrasonic disperse in absolute ethyl alcohol; Add 3-aminopropyl triethoxysilane, be heated with stirring to backflow, the upper end drying tube sealing that drying agent is housed of reflux, after reaction 12 ~ 24h, centrifuging product, obtains the pressed powder of the amination Nano particles of silicon dioxide of carbon coated point;
(2) structure of two transmitting composite silicon dioxide nano particle
The pressed powder of the amination Nano particles of silicon dioxide of carbon coated point is scattered in phosphate buffer; 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide and N-hydroxy-succinamide solution is added in gold nano cluster solution, stirred at ambient temperature 0.5 ~ 1h, adds the phosphate buffer of the amination Nano particles of silicon dioxide of carbon coated point wherein; After reaction 12-24h, centrifuging product, obtains two transmitting composite silicon dioxide nano particle, and is dispersed in ultrapure water;
(3) two transmitting composite silicon dioxide nano particle detects mercury ion
Standard solution containing mercury ion and solution to be measured being joined the two of step (2) gained launches in the aqueous solution of composite silicon dioxide nano particle, fluorescence spectrophotometer is utilized to measure fluorescence emission spectrum, record the fluorescence photo that lower pair of different mercury ion content launches composite silicon dioxide nano particle, and according to the fluorescence intensity of two emission peak than Criterion curve, contrast standard curve obtains the concentration of mercury ion in solution to be measured.
3. method as claimed in claim 2, it is characterized in that, in described step (1), the volume ratio of described cyclohexane, triton x-100, n-hexyl alcohol, water, ethyl orthosilicate, carbon quantum dot and ammoniacal liquor is 152:35.4:35.4:7.6:1:0.5:4.
4. method as claimed in claim 2, it is characterized in that in described step (2), the concentration of 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide is 50 ~ 100mmol/L, and the concentration of N-hydroxy-succinamide solution is 100 ~ 500mmol/L.
5. method as claimed in claim 2, is characterized in that, in described step (2), the mol ratio of 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide and N-hydroxy-succinamide is 1:4.
6. method as claimed in claim 2, it is characterized in that, in described step (2), the pH value of phosphate buffer is 6.5 ~ 7.0, the concentration of phosphate buffer is 10 ~ 50mmol/L.
7. method as claimed in claim 2, is characterized in that the maximum emission wavelength of carbon point is 350-550nm.
8. method as claimed in claim 2, is characterized in that the maximum emission wavelength of gold nano cluster is 580-670nm.
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