CN106833646A - A kind of ratio fluorescent probe and its preparation and application based on ion blotting - Google Patents
A kind of ratio fluorescent probe and its preparation and application based on ion blotting Download PDFInfo
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- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
- C09K11/881—Chalcogenides
- C09K11/883—Chalcogenides with zinc or cadmium
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- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
Abstract
The invention discloses a kind of ratio fluorescent probe based on ion blotting and its preparation and application, the fluorescence probe is with red quantum dot as core and is embedded in silica dioxide nano particle, amination modification is carried out to silica dioxide nano particle surface again, then green quantum dot on surface covalent coupling again after amination modification, obtains the ratio fluorescent probe based on ion blotting.Ratio-type ion blotting of the ratio fluorescent probe of the present invention based on quantum dot detects metal ion, with quite outstanding specificity.And good stability, the advantages of prepare simple, cheap, and the reaction time is substantially reduced, to the detection as little as 25nM of cadmium ion, it is convenient that quick visualization detection is provided.
Description
(1) technical field
The present invention relates to a kind of preparation for the quick visualization ratio fluorescent probe of cadmium ion detection in water and detection
Method.
(2) background technology
Cadmium is a kind of toxic heavy metal, is prevalent in industrial, contaminated agricultural product and our daily lifes.When
After environment is subject to cadmium pollution, cadmium can be enriched with vivo.Cadmium can enter human body by food chain, with the sulfydryl on protein
With reference to, cadmium sulfoprotein is formed, optionally accumulate in liver, kidney, cause a series of acute and chronic diseases, such as osteoporosis, lung cancer
Deng.Therefore we facilitate feasible method to detect Cd in the urgent need to development is a kind of2+.Traditional Cd2+Detection method, such as atom
Absorption spectrum, inductive coupling plasma mass spectrometry, particle induction x-ray fluorescence analysis, chromatography and voltammetry test fee are high, sample
Complex pretreatment, the testing time is long.
Detect that heavy metal ion has the advantages that simple and convenient, sensitivity is high, the response time is short using the method for fluorescence,
It is frequently utilized for quick visualization detection.However, most fluorescence probe is only detected with single chemical signal at present,
During detection, easily influenceed by incident light, concentration and probe concentration and environmental change, and caused result distortion, sensitivity is declined.Closely
Nian Lai, scientific workers have developed Ratio-type probe.Ratio probes possess two signals independent mutually, have both improve sensitive
Degree, realizes the function of self and visualization discriminance analysis thing again.Organic dyestuff and quantum dot are usually used to provide ratio
The fluorescence signal of probe, compared to organic dyestuff, quantum dot have that quantum efficiency is high, light resistance is good, emission spectrum is narrow and it is symmetrical,
The advantages of absorption spectrum is wide, size is controllable.Therefore, in the past few years, the ratio probes based on quantum dot have been obtained comparatively fast
Development, and be usually used in detect metal ion.
So far, the Chinese patent report about the ratio probes of cadmium ion has (CN102936501A), and the method is
A kind of " off/on " model probe.During the probe in detecting cadmium ion, it is impossible to efficiently differentiate zinc ion and cadmium ion.Molecular engram
It is for improving selective a kind of good method, can be used to specific recognition compound.Molecular engram probe has stability
Well, the advantages of preparing simple, cheap, is usually used to detection agricultural chemicals, insecticide, explosive etc. in recent years.Inspired by this, be
The selectivity of cadmium ion detection is improved, we design and synthesized a kind of ion blotting probe.As far as we know, there is presently no
The quantum dot ratio fluorescent probe based on ion blotting was reported to detect cadmium ion.
(3) content of the invention
Cadmium ion probe the present invention seeks to overcome the shortcomings of to be currently based on quantum dot, there is provided one kind prepare simply, into
This is cheap, easy to detect, the ratio fluorescent probe of selectivity preferably detection cadmium ion, realizes quick to the selectivity of cadmium ion
Visual retrieval.
The technical solution adopted by the present invention is：
The present invention provides a kind of ratio fluorescent probe based on ion blotting, and the fluorescence probe is with red quantum dot as core
The heart is simultaneously embedded in silica dioxide nano particle, then carries out amination modification to silica dioxide nano particle surface, then again in amino
Change green quantum dot on the surface covalent coupling after modification, obtain the ratio fluorescent probe based on ion blotting.
Further, preferably described red quantum dot is cadmium telluride quantum dot.
Further, preferably described green quantum dot is CdSe quantum dots.
Further, preferably it is described embedding silica dioxide nano particle red quantum dot particle diameter be 40-100nm, preferably 40~
60nm。
The present invention also provides a kind of preparation method of the ratio fluorescent probe based on ion blotting, and methods described is：
(1) red quantum dot is scattered in ammoniacal liquor (mass concentration 25%), NaOH and deionized water, 5~45 DEG C stirring 0.1~
1h (preferably 25 DEG C stirring 0.5h), forms quantum dot aqueous slkali；The red quantum dot is 1 with NaOH mass ratio：0.2~
1 (preferably 1:0.6), the ammoniacal liquor volumetric usage is calculated as 4~40ml/g (preferably 22ml/g), deionization with red quantum point mass
Water volume consumption is calculated as 500~1000ml/g (preferably 978ml/g) with red quantum point mass；(2) by hexamethylene, n-hexyl alcohol and
Qula is logical to be mixed and stirred for transparent, is subsequently adding 5~20mM polydiene dipropyl aqueous ammonium chloride solutions and ammoniacal liquor (mass concentration
25%) microemulsion system, is formed；In the microemulsion system, hexamethylene, n-hexyl alcohol, Qula are logical, polydiene dipropyl ammonium chloride solution
The volume final concentration of liquid and ammoniacal liquor is respectively 60~90%, 6~20%, 10~25%, 0.01~1%, 0.1~1%；(3) will
Step (1) quantum dot aqueous slkali is added in step (2) microemulsion system, 5~45 DEG C of 10~60min of stirring (preferably 25 DEG C stirrings
0.5h), reverse microemulsion system is formed；Then to addition tetraethyl orthosilicate (TEOS), then 5~45 DEG C in reverse microemulsion system
Stirring (preferably 25 DEG C stirring 2d) addition 3- aminopropyl triethoxysilanes (APTES) afterwards in 1~4 day, continuation stirring mixing 12~
24h, centrifugation, precipitation is washed 1~2 time with isopropanol, absolute ethyl alcohol, deionized water successively, obtains embedding the two of red quantum dot
Silicon oxide nanoparticle (i.e. CdTe@SiO2-NH2)；The quantum dot aqueous slkali is 1 with microemulsion system volume ratio：5~30 (preferably
1:11.17)；The tetraethyl orthosilicate is 0.01~2 with quantum dot aqueous slkali volume ratio：1 (preferably 0.1:1)；The 3- ammonia
Propyl-triethoxysilicane is 0.001~0.1 with quantum dot aqueous slkali volume ratio：1 (preferably 0.01:1)；(4) step (3) is made
The Nano particles of silicon dioxide of standby embedding red quantum dot forms dispersion liquid in being distributed to deionized water, and adds green quantum
Select and pH=7.0 PB buffer solutions, dark 8 hours of stirring, centrifugation, precipitation is washed with deionized, obtain it is described be based on from
The cadmium ion ratio fluorescent probe of sub- trace；The green quantum dot and the Nano particles of silicon dioxide matter for embedding red quantum dot
Amount is than being 0.05~1：1 (preferably 0.3:1), the PB buffer solutions volumetric usage is embedding the silica nanometer of red quantum dot
Mass particle is calculated as 10~100ml/g (preferably 38.4ml/g).
Further, preferred steps (1) red quantum dot and NaOH mass ratio are 1：0.6~0.8, the ammoniacal liquor
Volumetric usage is calculated as 20~25ml/g with red quantum point mass.
Further, in preferred steps (2) described microemulsion system, hexamethylene, n-hexyl alcohol, Qula are logical, polydiene dipropyl chlorine
The volume final concentration for changing aqueous ammonium and ammoniacal liquor is respectively 60~70%, 15~20%, 15~18%, 0.2~0.4%, 0.5~
0.6%.
Further, preferred steps (3) the quantum dot aqueous slkali and microemulsion system volume ratio are 1：10~15；The positive silicon
Sour tetra-ethyl ester is 0.1~0.5 with quantum dot aqueous slkali volume ratio：1；The 3- aminopropyl triethoxysilanes and quantum dot alkali soluble
Liquid volume ratio is 0.01~0.02：1.
Further, preferred steps (4) the green quantum dot and the Nano particles of silicon dioxide matter for embedding red quantum dot
Amount is than being 0.3~0.5：1, the PB buffer solutions volumetric usage is in terms of the Nano particles of silicon dioxide quality for embedding red quantum dot
It is 35~40ml/mg.
Additionally, the present invention also provides a kind of ratio fluorescent probe based on ion blotting answering in cadmium ion is detected
With.Specific method is：The ratio probe of 200 0~0.2g/ml of μ L concentration ranges, the Tris-HCl bufferings in pH intervals 6.0~10.0
The EDTA aqueous solution of the μ L of liquid 200 and 80 0~10 μM of μ L concentration ranges is added in probe tube, adds the Cd containing 0~30 μM of concentration2+
Water sample, be finally diluted to 2mL with deionized water, fluorometric investigation is carried out after 10 minutes under testing conditions same as described above.
In order to further probe into the selectivity of cadmium ion ratio fluorescent probe of the present invention based on ion blotting, we are visiting
A series of metal ion, including Zn are added in the dispersion liquid of pin2+、Mg2+、Ba2+、Cu2+、Ni2+、Hg2+、Co2+、K+、Ca2+、Fe3 +、Ag+And Mn2+, and carry out fluorescence spectrum detection, by contrast, Mg2+、Ba2+、Ni2+、Co2+、K+、Ca2+And Zn2+To ion blotting
The fluorescence influence of probe is little, Cu2+、Hg2+、Fe3+、Ag+、Mn2+Quenching of fluorescence, fluorescence color can be caused to become laking.Cause
This, the ratio probes that we synthesize remain able to optionally detect Cd2+。
Compared with prior art, the beneficial effects are mainly as follows：
1st, the Nano particles of silicon dioxide of the embedded quantum dots of red emission is prepared using reverse microemulsion method, compared to stober
Method, with more preferable dispersiveness, is conducive to the Nano particles of silicon dioxide surface amount of green color of the embedded quantum dots of red emission
The structure of son point layer, and quantum dot is formed into aqueous slkali, hatched, improve fluorescence property.
2nd, using the CdSe quantum dot of bistable as top layer quantum dot, compared to traditional cadmium telluride quantum dot, probe is steady
It is qualitative good.
3rd, compared to other ratio probes, in detection, Ratio-type ion blotting based on quantum dot is detected this probe
Metal ion, with quite outstanding specificity.And good stability, the advantages of prepare simple, cheap, and contract significantly
In the short reaction time, to the detection as little as 25nM of cadmium ion, it is convenient that quick visualization detection is provided.
(4) illustrate
Fig. 1 is the TEM figures of the Nano particles of silicon dioxide of the embedded quantum dots of red emission in embodiment 1.
Fig. 2 is the TEM figures of ratio probes in embodiment 1.
Fig. 3 is fluorescence spectra in embodiment 3.
Fig. 4 is corresponding fluorescence photo under 365nm uviol lamps in embodiment 3, from left to right Cd2+Concentration is followed successively by 0,1,2,
3、4、5、6、7、8、9μM。
Fig. 5 is fluorescence spectra in embodiment 4.
Fig. 6 is corresponding fluorescence photo under 365nm uviol lamps in embodiment 4, be followed successively by from left to right blank, 10 μM
Cd2+、Zn2+、Mg2+、Ba2+、Cu2+、Ni2+、Hg2+、Co2+、K+、Ca2+、Fe3+、Ag+、Mn2+。
(5) specific embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This：
Poly- two propylene diethylammonium chloride molecular weight is 100000~200000 used by the embodiment of the present invention.
Embodiment 1：
1st, the preparation of red quantum dot
By 0.2284g caddies (CdCl2·2.5H2O) it is added in 500mL deionized waters, leads to nitrogen 20min, then adds
Enter 0.1mL mercaptopropionic acids, then pH is adjusted to 11.00 with the sodium hydrate aqueous solution of 1M, then proceed to add 0.538g citric acids
Sodium (contains the crystallization water), and 0.0444g sodium tellurites, 0.2g sodium borohydrides are finally heated to reflux.It is red transmitting to be obtained after backflow 8h
The cadmium telluride quantum dot aqueous solution (i.e. red quantum dot solution) of the mercaptopropionic acid stabilization of color fluorescence, emission peak is dense at 628 nanometers
Spend is 4.3 × 10-6mol/L。
Take the red quantum dot solution that 4mL has synthesized, add 4mL absolute ethyl alcohols, staticly settle, be centrifuged, precipitation is with anhydrous
Ethanol is washed 1~2 time, obtains cadmium telluride red quantum dot 3mg.
2nd, the Nano particles of silicon dioxide of red quantum dot is embedded
Take 1mg red quantum dots and be scattered in 0.022ml ammoniacal liquor (25wt%) and 0.6mg NaOH, 0.978mL go from
In sub- water, 25 DEG C of stirrings 30min, as red quantum dot aqueous slkali 1ml, the wherein final concentration of 0.6wt% of ammoniacal liquor quality, hydrogen-oxygen
Change the final concentration of 15.9mmol/L of sodium, the final concentration of 1mg/ml of red quantum dot.Hexamethylene 7.5mL, n-hexyl alcohol 1.8mL are taken, it is bent
Draw logical 1.77mL to be mixed and stirred for forming transparent mixed solution, 60 μ L ammoniacal liquor are then added in transparent mixed solution
(25wt%), 40 μ L concentration are the polydiene dipropyl aqueous ammonium chloride solution of 1.78mmol/L, form microemulsion system 11.17ml.
Then red quantum dot aqueous slkali 1ml is added in above-mentioned 11.17ml microemulsion systems, 25 DEG C of stirring 30min obtain transparent
Reverse microemulsion body.Then to 100 μ L tetraethyl orthosilicates are added in reverse microemulsion system, 25 DEG C of stirrings add 10 μ L two days later
3- aminopropyl triethoxysilanes (APTES), continue stir 24h after be centrifuged, precipitation successively with isopropanol, absolute ethyl alcohol, go from
Sub- water washing 1~2 time, obtains embedding Nano particles of silicon dioxide (the i.e. CdTe@SiO of red quantum dot2-NH2) 0.012g, grain
40~60nm of footpath (shape appearance figure is shown in Fig. 1).The Nano particles of silicon dioxide of the embedding red quantum dot that will be obtained is dispersed in deionization
It is standby in water.
3rd, the cadmium ion ratio fluorescent probe based on ion blotting
The CdSe aqueous solution (being diluted with water from 5mL CdSe quantum dot stostes, quality is 0.004g) of 2mL is added to
2mL CdTe@SiO2-NH2In (13mg) dispersion liquid, the caching PB buffer solutions of 0.5mL pH=7.0 are subsequently added into, in dark condition
Lower stirring 8h.After reaction terminates, centrifugation takes and precipitates and be washed with deionized 3 times, removes unnecessary quantum dot, obtains 1mg/
The CdTe@SiO of ml2@CdSe ratio probes, under 365nm uviol lamps, fluorescence is in green (shape appearance figure is shown in Fig. 2).To finally obtain
CdTe@SiO2@CdSe Nano microspheres disperse in deionized water, and are stored in 4 DEG C of refrigerator, standby.
Embodiment 2：
1st, the preparation of red quantum dot
By 0.2284g caddies (CdCl2·2.5H2O) it is added in 500mL deionized waters, leads to nitrogen 20min, then adds
Enter 0.1mL mercaptopropionic acids, then pH is adjusted to 11.00 with the sodium hydrate aqueous solution of 1M, then proceed to add 0.538g citric acids
Sodium (contains the crystallization water), and 0.0444g sodium tellurites, 0.2g sodium borohydrides are finally heated to reflux.It is red transmitting to be obtained after backflow 8h
The cadmium telluride quantum dot aqueous solution (i.e. red quantum dot solution) of the mercaptopropionic acid stabilization of color fluorescence, emission peak is dense at 628 nanometers
Spend is 4.3 × 10-6mol/L。
Take the red quantum dot solution that 4mL has synthesized, add 4mL absolute ethyl alcohols, staticly settle, be centrifuged, precipitation is with anhydrous
Ethanol is washed 1~2 time, obtains cadmium telluride red quantum dot 3mg.
2nd, the Nano particles of silicon dioxide of red quantum dot is embedded
Take 1mg red quantum dots and be scattered in 0.022ml ammoniacal liquor (25wt%) and 0.8mg NaOH, 0.978mL go from
In sub- water, 25 DEG C of stirrings 30min, as red quantum dot aqueous slkali 1ml, the wherein final concentration of 0.6wt% of ammoniacal liquor quality, hydrogen-oxygen
Change the final concentration of 21.2mmol/L of sodium, the final concentration of 1mg/ml of red quantum dot.Hexamethylene 6.8mL, n-hexyl alcohol 2.2mL are taken, it is bent
Draw logical 2.0mL to be mixed and stirred for forming transparent mixed solution, 60 μ L ammoniacal liquor (25wt%) then added in transparent mixed solution,
40 μ L concentration are the polydiene dipropyl aqueous ammonium chloride solution of 1.78mmol/L, form microemulsion system 11.1ml.Then by red
Quantum dot aqueous slkali 1ml is added in above-mentioned 11.1ml microemulsion systems, 25 DEG C of stirring 30min, obtains transparent reverse microemulsion body.
Then to 500 μ L tetraethyl orthosilicates are added in reverse microemulsion system, 25 DEG C of stirrings add the second of 20 μ L 3- aminopropyls three two days later
TMOS (APTES), continues to be centrifuged after stirring 24h, and precipitation washs 1~2 with isopropanol, absolute ethyl alcohol, deionized water successively
It is secondary, obtain embedding Nano particles of silicon dioxide (the i.e. CdTe@SiO of red quantum dot2-NH2) 0.012g, 40~60nm of particle diameter.Will
The Nano particles of silicon dioxide dispersion of the embedding red quantum dot for obtaining is in deionized water, standby.
3rd, the cadmium ion ratio fluorescent probe based on ion blotting
The CdSe aqueous solution (deriving from 8mL CdSe quantum dot stostes, quality is 0.0065g) of 2mL is added to 2mL
CdTe@SiO2-NH2In (13mg) dispersion liquid, the caching PB buffer solutions of 0.5mL pH=7.0 are subsequently added into, are stirred under dark condition
Mix 8h.After reaction terminates, centrifugation takes and precipitates and be washed with deionized 3 times, removes unnecessary quantum dot, obtains 1mg/ml's
CdTe@SiO2@CdSe ratio probes, under 365nm uviol lamps, fluorescence is in green.The CdTe@SiO that will finally obtain2@CdSe nanometers
Microballoon disperses in deionized water, and is stored in 4 DEG C of refrigerator, standby.
Embodiment 3：
1st, the preparation of red quantum dot
By 0.4568g caddies (CdCl2·2.5H2O) it is added in 500mL deionized waters, leads to nitrogen 20min, then adds
Enter 0.2mL mercaptopropionic acids, then pH is adjusted to 11.00 with the sodium hydrate aqueous solution of 1M, then proceed to add 1.076g citric acids
Sodium (contains the crystallization water), and 0.0888g sodium tellurites, 0.4g sodium borohydrides are finally heated to reflux.It is red transmitting to be obtained after backflow 8h
The cadmium telluride quantum dot aqueous solution (i.e. red quantum dot solution) of the mercaptopropionic acid stabilization of color fluorescence, emission peak is dense at 628 nanometers
Spend is 6.5 × 10-6mol/L。
Take the red quantum dot solution that 2mL has synthesized, add 2mL absolute ethyl alcohols, staticly settle, be centrifuged, precipitation is with anhydrous
Ethanol is washed 1~2 time, obtains cadmium telluride red quantum dot 2.8mg.
2nd, the Nano particles of silicon dioxide of red quantum dot is embedded
Take 1mg red quantum dots and be scattered in 0.025ml ammoniacal liquor (25wt%) and 0.6mg NaOH, 0.975mL go from
In sub- water, 25 DEG C of stirrings 30min, as red quantum dot aqueous slkali 1ml, the wherein final concentration of 0.625wt% of ammoniacal liquor quality, hydrogen
The final concentration of 15.9mmol/L of sodium oxide molybdena, the final concentration of 1mg/ml of red quantum dot.Hexamethylene 7.8mL, n-hexyl alcohol 1.7mL are taken,
The logical 1.7mL of Qula is mixed and stirred for forming transparent mixed solution, and 60 μ L ammoniacal liquor are then added in transparent mixed solution
(25wt%), 40 μ L concentration are the polydiene dipropyl aqueous ammonium chloride solution of 1.78mmol/L, form microemulsion system 11.3ml.So
Red quantum dot aqueous slkali 1ml is added in above-mentioned 11.3ml microemulsion systems afterwards, 25 DEG C of stirring 30min obtain transparent anti-
Phase micro emulsion body.Then to 500 μ L tetraethyl orthosilicates are added in reverse microemulsion system, 25 DEG C of stirrings add 10 μ L 3- two days later
Aminopropyl triethoxysilane (APTES), continues to be centrifuged after stirring 24h, and precipitation uses isopropanol, absolute ethyl alcohol, deionization successively
Water washing 1~2 time, obtains embedding Nano particles of silicon dioxide (the i.e. CdTe@SiO of red quantum dot2-NH2) 0.012g, particle diameter
40~60nm.The Nano particles of silicon dioxide dispersion of the embedding red quantum dot that will be obtained is in deionized water, standby.
3rd, the cadmium ion ratio fluorescent probe based on ion blotting
The CdSe aqueous solution (deriving from 5mL CdSe quantum dot stostes, quality is 0.004g) of 2mL is added to 2mL CdTe@
SiO2-NH2In (12mg) dispersion liquid, the caching PB buffer solutions of 0.5mL pH=7.0 are subsequently added into, 8h is stirred under dark condition.
After reaction terminates, centrifugation takes and precipitates and be washed with deionized 3 times, removes unnecessary quantum dot, obtains the CdTe@of 1mg/ml
SiO2@CdSe ratio probes, under 365nm uviol lamps, fluorescence is in green.The CdTe@SiO that will finally obtain2@CdSe Nano microspheres
Dispersion in deionized water, and is stored in 4 DEG C of refrigerator, standby.
Embodiment 4：Cd in buffer solution2+Detection
The ratio probes deionized water suspension for adding the embodiment 1 that 200 μ L concentration are 0.5mg/mL to prepare in probe tube,
200 μ L concentration are the Tris-HCl buffer solutions of 100mM, pH=9, and 80 μ L concentration are the EDTA aqueous solution of 0.02mM, then
Add the Cd of different final concentrations2+(0,1,2,3,4,5,6,7,8,9 μM), are finally diluted to 2mL, and shake up with deionized water.10
Mixed liquor is transferred in 3mL cuvettes after minute carry out fluoroscopic examination, according to the contrast of color in probe tube, it can be determined that no
With Cd in probe tube2+Concentration, Cd2+Concentration it is bigger, fluorescence get over be partial to green (fluorogram is shown in Fig. 3, under 365nm uviol lamps
Corresponding fluorescence photo is shown in Fig. 4).All of operation is carried out at room temperature, and the condition of fluoroscopic examination is as follows：Excitation wavelength is
The slit width of 380nm, exciting light and launching light is 3nm, and sweep limits is from 450nm to 740nm.
Embodiment 5：Cd in actual water body example2+Detection
In order to assess the practicality of ratio probes, we carry out Cd with two kinds of actual water samples of lake water and running water2+Detection is real
Test.Lake water used takes from the bank at 100 meters of West Lake music fountain south in experiment, is filtered with 0.22 μm of filter before experiment
2 times, remove the suspension in the water of the West Lake.Originally water sample is directly obtained from the tap in laboratory, and any pre-treatment is not done.
When actually detected, the ratio probes deionized water suspension that 200 μ L concentration are prepared for the embodiment 1 of 0.5mg/mL, 200 μ L concentration
It is the Tris-HCl buffer solutions of 100mM, pH=9, and the EDTA aqueous solution that 80 μ L concentration are 0.02mM is added in probe tube,
It is subsequently adding the Cd that 1mL contains various concentrations2+Running water and West Lake water sample (West Lake water sample is first filtered out before the use
Solid suspension in water, originally water sample is preceding without any treatment in use, then each adds a certain amount of Cd2+, make sample
Product contain Cd2+Concentration is 2.0,5.0 and 8.0 μM), 2mL finally is diluted to deionized water, in inspection same as described above after 10 minutes
Fluorometric investigation is carried out under the conditions of survey, according to the fluorescence color of probe tube, you can judge Cd2+Concentration, Cd2+Concentration it is bigger, it is glimmering
Light is got over and is partial to green.
The selectivity of the ion blotting ratio probes of embodiment 6
In order to further probe into Cd2+The selectivity of trace ratio probes, we add a series of in the dispersion liquid of probe
Metal ion, including Zn2+、Mg2+、Ba2+、Cu2+、Ni2+、Hg2+、Co2+、K+、Ca2+、Fe3+、Ag+And Mn2+, and by fluorescence
Spectrum, records the situation of change of ratio fluorescent.
14 probe tubes are taken, ratio prepared by the embodiment 1 that 200 μ L concentration are 0.5mg/mL is separately added into probe tube
Probe deionized water suspension, the Tris-HCl buffer solutions of 0.01M, pH9.0 and 80 μ L concentration are the EDTA aqueous solution of 0.02mM, are connect
It is blank with first probe tube, and the Cd that metal ion final concentration is followed successively by 10 μM is separately added into other probe tubes2+、
Zn2+、Mg2+、Ba2+、Cu2+、Ni2+、Hg2+、Co2+、K+、Ca2+、Fe3+、Ag+、Mn2+, 2mL finally is diluted to deionized water, and
Shake up.Being transferred to mixed liquor after 10 minutes in the cuvette of 3mL carries out fluoroscopic examination (fluorescence spectra is shown in Fig. 5, and 365nm is purple
Corresponding fluorescence photo is shown in Fig. 6 under outer lamp), by corresponding fluorescence photo, it can be seen that only added Cd2+Sample, fluorescence
Green is just changed to by red, the ion blotting ratio probes is also accordingly demonstrated to Cd2+Selectivity.
Claims (10)
1. a kind of ratio fluorescent probe based on ion blotting, it is characterised in that the fluorescence probe is with red quantum dot as core
And be embedded in silica dioxide nano particle, then amination modification is carried out to silica dioxide nano particle surface, then again in amination
Green quantum dot, obtains the ratio fluorescent probe based on ion blotting on surface covalent coupling after modification.
2. the ratio fluorescent probe of ion blotting is based on as claimed in claim 1, it is characterised in that the red quantum dot is tellurium
Cadmium quantum dot.
3. the ratio fluorescent probe of ion blotting is based on as claimed in claim 1, it is characterised in that the green quantum dot is selenium
Cadmium quantum dot.
4. the ratio fluorescent probe of ion blotting is based on as claimed in claim 1, it is characterised in that the embedding silica is received
The red quantum dot particle diameter of the grain of rice is 40~100nm.
5. the preparation method of the ratio fluorescent probe of ion blotting is based on described in a kind of claim 1, it is characterised in that the side
Method is：(1) red quantum dot is scattered in ammoniacal liquor, NaOH and deionized water, 5~45 DEG C of 0.1~1h of stirring, forming amount
Son point aqueous slkali；The red quantum dot is 1 with NaOH mass ratio：0.2~1, the ammoniacal liquor volumetric usage is with amount of red
Sub- point mass is calculated as 4~40ml/g, and deionized water volumetric usage is calculated as 500~1000ml/g with red quantum point mass；(2) will
Hexamethylene, n-hexyl alcohol and Qula are logical to be mixed and stirred for transparent, is subsequently adding 5~20mM polydiene dipropyl aqueous ammonium chloride solutions
And ammoniacal liquor, form microemulsion system；In the microemulsion system, hexamethylene, n-hexyl alcohol, Qula are logical, polydiene dipropyl ammonium chloride water
The volume final concentration of solution and ammoniacal liquor is respectively 60~90%, 6~20%, 10~25%, 0.01~1%, 0.1~1%；(3)
Step (1) quantum dot aqueous slkali is added in step (2) microemulsion system, 5~45 DEG C of 10~60min of stirring are formed anti-phase micro-
Newborn system；Then to tetraethyl orthosilicate is added in reverse microemulsion system, then 5~45 DEG C of stirrings add 3- ammonia third after 1~4 day
Ethyl triethoxy silicane alkane, continues to stir 12~24h of mixing, and centrifugation, precipitation is washed with isopropanol, absolute ethyl alcohol, deionization successively
Wash 1~2 time, obtain embedding the Nano particles of silicon dioxide of red quantum dot；The quantum dot aqueous slkali and microemulsion system volume
Than being 1：5~30；The tetraethyl orthosilicate is 0.01~2 with quantum dot aqueous slkali volume ratio：1；The second of 3- aminopropyls three
TMOS is 0.001~0.1 with quantum dot aqueous slkali volume ratio：1；(4) by the embedding red quantum dot of step (3) preparation
Nano particles of silicon dioxide forms dispersion liquid in being distributed to deionized water, and adds the PB of green quantum dot and pH=7.0 to buffer
Liquid, dark 8 hours of stirring, centrifugation, precipitation is washed with deionized, and obtains the ratio fluorescent based on ion blotting and visits
Pin；The green quantum dot is 0.05~1 with the Nano particles of silicon dioxide mass ratio of embedding red quantum dot：1, the PB delay
Fliud flushing volumetric usage is calculated as 10~100ml/g to embed the Nano particles of silicon dioxide quality of red quantum dot.
6. the preparation method of the ratio fluorescent probe of ion blotting is based on as claimed in claim 5, it is characterised in that step (1) institute
It is 1 that red quantum dot is stated with NaOH mass ratio：0.6~0.8, the ammoniacal liquor volumetric usage is calculated as with red quantum point mass
20~25ml/g.
7. the preparation method of the ratio fluorescent probe of ion blotting is based on as claimed in claim 5, it is characterised in that step (2) institute
In stating microemulsion system, hexamethylene, n-hexyl alcohol, Qula are logical, the volume final concentration of polydiene dipropyl aqueous ammonium chloride solution and ammoniacal liquor
Respectively 60~70%, 15~20%, 15~18%, 0.2~0.4%, 0.5~0.6%.
8. the preparation method of the ratio fluorescent probe of ion blotting is based on as claimed in claim 5, it is characterised in that step (3) institute
It is 1 that quantum dot aqueous slkali is stated with microemulsion system volume ratio：10~15；The tetraethyl orthosilicate is with quantum dot aqueous slkali volume ratio
0.1~0.5：1；The 3- aminopropyl triethoxysilanes are 0.01~0.02 with quantum dot aqueous slkali volume ratio：1.
9. the preparation method of the ratio fluorescent probe of ion blotting is based on as claimed in claim 5, it is characterised in that step (4) institute
It is 0.3~0.5 that green quantum dot is stated with the Nano particles of silicon dioxide mass ratio of embedding red quantum dot：1, the PB buffer solutions
Volumetric usage is calculated as 35~40ml/g to embed the Nano particles of silicon dioxide quality of red quantum dot.
10. application of the ratio fluorescent probe based on ion blotting in cadmium ion is detected described in a kind of claim 1.
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Non-Patent Citations (1)
| Title |
|---|
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