CN104655604B - It is a kind of to be used to detect fluorescent optical sensor of fluorine ion and preparation method thereof - Google Patents
It is a kind of to be used to detect fluorescent optical sensor of fluorine ion and preparation method thereof Download PDFInfo
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- CN104655604B CN104655604B CN201510079623.7A CN201510079623A CN104655604B CN 104655604 B CN104655604 B CN 104655604B CN 201510079623 A CN201510079623 A CN 201510079623A CN 104655604 B CN104655604 B CN 104655604B
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Abstract
The invention discloses a kind of fluorescent optical sensor for being used to detect fluorine ion and preparation method thereof, preparation method includes：3 amino phenyl boric acids are soluble in water and pH value of regulation system is alkalescence, hydro-thermal reaction is then carried out, carbon point is obtained；In the HAuCl4 solution that sodium citrate solution is added to boiling, it is stirred at reflux to system and takes on a red color, then obtains nanogold through cooling, centrifugation, washing；After the propane diols of 3 sulfydryl 1,2 and nanogold are mixed react obtaining modified nano gold；Carry out reacting after carbon point is mixed with modified nano gold and obtain the fluorescent optical sensor for being used to detect fluorine ion.The preparation method of the present invention for being used to detect the fluorescent optical sensor of fluorine ion, process is simple and easy to apply, environmental protection, extend to the preparation of other Illuminant nanometer materials, what is obtained is used for the fluorine ion for detecting that the fluorescent optical sensor of fluorine ion can be used in the detection aqueous solution, toxicity is low, and quantum yield is high, photostability, biocompatibility and sensitivity are good.
Description
Technical field
The present invention relates to technical field of analytical chemistry, more particularly to a kind of fluorescent optical sensor for being used to detect fluorine ion and its
Preparation method.
Background technology
Fluorine is one of necessary trace element of human body, is the required material for maintaining bone and tooth growth.Meet human body needs
The amount of fluorine ion and due to fluorine it is excessive caused by fluorine poisoning amount between be more or less the same, so strictly grasp fluorine intake ten
Divide important, otherwise easily cause fluorine poisoning.At present, the detection method of fluorine ion is most commonly used that AAS and fluorine ion selection
Property electrode method.In AAS, the polyenergetic of photometer light source, presence of the solution to disturbing factors such as the scatterings of light,
Measurement result will be made to deviate Lambert-Beer laws, measurement accuracy is directly affected, and fluoride ion selective electrode is easily dirty
Contaminate, zero point and full scale need the application of often adjustment demarcation, working service cost height, therefore both approaches all by certain
The limitation of degree.Fluorescent optical sensor has high simple to operate, selectivity, sensitivity height, instantaneity strong, detects low, signal of limiting the quantity
It is directly perceived simple, disturb small, it is easy to the advantage of discrimination, the study hotspot in recent years as detection fluorine ion.
In past twenties years, because nano material has its unique optics, electricity and magnetic property, cause
Strong interest to building chemical sensor based on nano material, these open one based on the sensor that nano material is built
New era that is simple, sensitive and detecting on the spot is carried out to special objective thing.Quantum dot due to quantum yield it is high, excite and send out
Penetrate the advantage of tunable wave length, it has also become detection nucleic acid, enzyme, protein, metal ion and other small molecules etc. make the most extensively
Optical nano material.However, quantum dot also has toxicity in the case that concentration is very low.In addition, quantum dot is usual
Organic solvent is dissolved in, so as to greatly limit its application in analysis detection field.
The content of the invention
The present invention proposes a kind of preparation method for being used to detect the fluorescent optical sensor of fluorine ion, and this method process is simply easy
Row, environmental protection, extend to the preparation of other Illuminant nanometer materials；It is used to detect fluorine ion the invention also provides a kind of
Fluorescent optical sensor, its fluorine ion that can be used in the detection aqueous solution, toxicity is low, and quantum yield is high, photostability, bio-compatible
Property and sensitivity are good.
The present invention proposes a kind of preparation method for being used to detect the fluorescent optical sensor of fluorine ion, comprises the following steps：
It is S1,3- amino phenyl boric acids is soluble in water and pH value of regulation system is alkalescence, hydro-thermal reaction is then carried out, is reacted
After end carbon point is obtained through cooling, centrifugation, dialysis；
S2, the HAuCl by sodium citrate solution addition boiling4In solution, it is stirred at reflux to system and takes on a red color, then through cold
But, centrifuge, washing obtains nanogold；
S3, will 3- sulfydryl -1,2- propane diols and nanogold mix after react obtaining modified nano gold；
S4, carbon point is mixed with modified nano gold after react and obtain the fluorescence sense for being used to detect fluorine ion
Device.
Preferably, it is in S1,3- amino phenyl boric acids is soluble in water and pH value of regulation system is 8-10；
Preferably, it is in S1,3- amino phenyl boric acids is soluble in water and pH value of regulation system is 8-9；
Preferably, it is in S1,3- amino phenyl boric acids is soluble in water and pH value of regulation system is 9.
Preferably, in S1, the temperature of the hydro-thermal reaction is 145-180 DEG C, and the time of hydro-thermal reaction is 8-10h；
Preferably, in S1, the temperature of the hydro-thermal reaction is 150-170 DEG C, and the time of hydro-thermal reaction is 8.5-9.5h；
Preferably, in S1, the temperature of the hydro-thermal reaction is 160 DEG C, and the time of hydro-thermal reaction is 9h.
Preferably, in S1, in dialysis procedure, the bag filter dialysis 20-28h for carrying and staying molecular weight for 800-1200 is used；
Preferably, in S1, in dialysis procedure, the bag filter dialysis 22-26h for carrying and staying molecular weight for 900-1100 is used；
Preferably, in S1, in dialysis procedure, use carry stay molecular weight be 1000 bag filter dialysis 24h.
Preferably, in S2, the mass fraction of sodium citrate is 0.8-1.2%, HAuCl in sodium citrate solution4Solution
Middle HAuCl4Mass fraction be 0.008-0.012%, sodium citrate solution and HAuCl4The volume ratio of solution is 5-6:130-
180；
Preferably, in S2, the mass fraction of sodium citrate is 0.9-1.1%, HAuCl in sodium citrate solution4Solution
Middle HAuCl4Mass fraction be 0.009-0.011%, sodium citrate solution and HAuCl4The volume ratio of solution is 5.2-5.8:
150-170；
Preferably, in S2, the mass fraction of sodium citrate is 1%, HAuCl in sodium citrate solution4HAuCl in solution4
Mass fraction be 0.01%, sodium citrate solution and HAuCl4The volume ratio of solution is 5.25:150.
Preferably, in S3, the ratio between volume of 3- sulfydryls -1,2-PD and nanogold is 1:3500-4500；
Preferably；In S3, the ratio between volume of 3- sulfydryls -1,2-PD and nanogold is 1:3800-4200；
Preferably, in S3, the ratio between volume of 3- sulfydryls -1,2-PD and nanogold is 1:4000.
Preferably, in S3, the reaction time reacted after 3- sulfydryls -1,2-PD and nanogold mixing is 7-
13h；
Preferably, in S3, the reaction time reacted after 3- sulfydryls -1,2-PD and nanogold mixing is 8-
12h；
Preferably, in S3, the reaction time reacted after 3- sulfydryls -1,2-PD and nanogold mixing is 10h.
Preferably, in S4, the volume ratio of carbon point and modified nano gold is 1:15-22；
Preferably, in S4, the volume ratio of carbon point and modified nano gold is 1:18-20；
Preferably, in S4, the volume ratio of carbon point and modified nano gold is 1:20.
Preferably, it is described to be used to detect that the preparation method of the fluorescent optical sensor of fluorine ion comprises the following steps：
S1, the 3- amino phenyl boric acids of 0.08-0.12 parts by weight are dissolved in the water of 15-22 parts by weight, the pH of regulation system
It is worth for 8-10, then carries out hydro-thermal reaction, wherein, the temperature of hydro-thermal reaction is 145-180 DEG C, and the time of hydro-thermal reaction is 8-
10h, reaction obtains carbon point after terminating through cooling, centrifugation, dialysis；
S2, by 130-180 parts by volume mass fraction be 0.008-0.012% HAuCl4Solution is heated to boiling, then
The sodium citrate solution that 5-6 parts by volume mass fraction is 0.8-1.2% is added, is stirred at reflux to system and takes on a red color, then through cold
But, centrifuge, washing obtains nanogold；
S3, will the 3- sulfydryl -1,2- propane diols of 1 parts by volume and 3500-4500 parts by volume nanogold mix after carry out it is anti-
7-13h is answered to obtain modified nano gold；
S4, the carbon point of 1 parts by volume is mixed with the modified nano gold of 15-22 parts by volume after carry out reaction 0.8-1.3h obtain
The fluorescent optical sensor for being used to detect fluorine ion；
Preferably, it is described to be used to detect that the preparation method of the fluorescent optical sensor of fluorine ion comprises the following steps：
S1, the 3- amino phenyl boric acids of 0.09-0.11 parts by weight are dissolved in the water of 19-21 parts by weight, the pH of regulation system
It is worth for 8-9, then carries out hydro-thermal reaction, wherein, the temperature of hydro-thermal reaction is 150-170 DEG C, and the time of hydro-thermal reaction is 8.5-
9.5h, reaction is cooled down after terminating, centrifugation, then stays the bag filter dialysis 20-28h that molecular weight is 800-1200 to obtain carbon with load
Point；
S2, by 150-170 parts by volume mass fraction be 0.009-0.011% HAuCl4Solution is heated to boiling, then
The sodium citrate solution that 5.2-5.8 parts by volume mass fraction is 0.9-1.1% is added, is stirred at reflux to system and takes on a red color, then
Nanogold is obtained through cooling, centrifugation, washing；
S3, will the 3- sulfydryl -1,2- propane diols of 1 parts by volume and 3800-4200 parts by volume nanogold mix after carry out it is anti-
8-12h is answered to obtain modified nano gold；
S4, the carbon point of 1 parts by volume is mixed with the modified nano gold of 18-20 parts by volume after carry out reaction 0.9-1.2h obtain
The fluorescent optical sensor for being used to detect fluorine ion；
Preferably, it is described to be used to detect that the preparation method of the fluorescent optical sensor of fluorine ion comprises the following steps：
S1, the 3- amino phenyl boric acids of 0.1 parts by weight are dissolved in the water of 20 parts by weight, utilize sodium hydroxide solution regulation body
The pH value of system is 9, then carries out hydro-thermal reaction, wherein, the temperature of hydro-thermal reaction is 160 DEG C, and the time of hydro-thermal reaction is 9h, instead
Room temperature is cooled to after should terminating, 30min is centrifuged under 10000r/min rotating speed, the dialysis for then staying molecular weight to be 1000 with carrying
Bag dialysis 24h obtains carbon point；
S2, by 150 parts by volume mass fractions be 0.01% HAuCl4Solution is heated to boiling, then adds 5.25 volumes
Part mass fraction is 1% sodium citrate solution, is stirred at reflux 15min and takes on a red color to system, then through cooling, centrifugation, washing
Obtain nanogold；
S3, will the 3- sulfydryl -1,2- propane diols of 1 parts by volume and 4000 parts by volume nanogold mix after carry out reaction 10h
Obtain modified nano gold；
S4, the carbon point of 1 parts by volume is mixed with the modified nano gold of 20 parts by volume after carry out reaction 1h and obtain described be used for
Detect the fluorescent optical sensor of fluorine ion.
The invention also provides a kind of fluorescent optical sensor for being used to detect fluorine ion, using described for detecting fluorine ion
The preparation method of fluorescent optical sensor be prepared from.
In the present invention, by selecting 3- amino phenyl boric acid to be raw material, the carbon containing boric acid base group has been synthesized using hydro-thermal method
Point, after modified nano gold is added, the boric acid base group on carbon point can connect with the 3- sulfydryls -1,2-PD on modified nano gold surface
Connect, carbon point and nanogold are combined as a whole, so as to cause the fluorescence of carbon point to be modified nanogold quenching；Add fluorine ion it
Afterwards, fluorine ion plays the role of stronger with boric acid base group so that 3- sulfydryl -1 on boric acid base group and modified nano gold on carbon point,
2- propane diols disconnects so that the fluorescence of carbon point recovers.
The preparation method of the present invention for being used to detect the fluorescent optical sensor of fluorine ion, process is simple and easy to apply, green ring
Protect, can be generalized to the synthesis field of other quantum dots, the obtained fluorescent optical sensor for being used to detect fluorine ion is examined to fluorine ion
Survey has specificity, the fluorine ion that can be used in the water pollution field detection aqueous solution, and toxicity is low, and quantum yield is high, and light is stable
Property and good biocompatibility.
Brief description of the drawings
Fig. 1 is fluorescent quenching figure of the modified nano gold (0-1.33nM) to carbon point of various concentrations in the present invention；
Fig. 2 is is used to detect fluoride solution (0-117 μ of the fluorescent optical sensor to various concentrations of fluorine ion in the present invention
M fluorescence response figure)；
Fig. 3 is is used to detect fluoride solution (9-117 μ of the fluorescent optical sensor to various concentrations of fluorine ion in the present invention
M) the linear relationship chart of fluorescence response.
Embodiment
The present invention is described in detail with reference to specific embodiment, it should be appreciated that embodiment is served only for illustrating this hair
It is bright, rather than for limiting the invention, any modification made on the basis of the present invention, equivalent substitution etc. are in this hair
In bright protection domain.
Embodiment 1
A kind of preparation method for being used to detect the fluorescent optical sensor of fluorine ion that the embodiment of the present invention is proposed, including following step
Suddenly：
S1, the 3- amino phenyl boric acids of 0.08 parts by weight are dissolved in the water of 22 parts by weight, the pH value of regulation system is 8, so
Laggard water-filling thermal response, wherein, the temperature of hydro-thermal reaction is 180 DEG C, and the time of hydro-thermal reaction is 8h, is reacted after terminating through cold
But, centrifuge, dialysing obtains carbon point；
S2, by 130 parts by volume mass fractions be 0.012% HAuCl4Solution is heated to boiling, then adds 5 parts by volume
Mass fraction is 1.2% sodium citrate solution, is stirred at reflux to system and takes on a red color, and is then received through cooling, centrifugation, washing
Meter Jin；
S3, will the 3- sulfydryl -1,2- propane diols of 1 parts by volume and 3500 parts by volume nanogold mix after carry out reaction 13h
Obtain modified nano gold；
S4, the carbon point of 1 parts by volume is mixed with the modified nano gold of 15 parts by volume after carry out reaction 0.8h obtain the use
In the fluorescent optical sensor of detection fluorine ion.
Embodiment 2
A kind of preparation method for being used to detect the fluorescent optical sensor of fluorine ion that the embodiment of the present invention is proposed, including following step
Suddenly：
S1, the 3- amino phenyl boric acids of 0.12 parts by weight are dissolved in the water of 15 parts by weight, the pH value of regulation system is 10, so
Laggard water-filling thermal response, wherein, the temperature of hydro-thermal reaction is 145 DEG C, and the time of hydro-thermal reaction is 10h, is reacted after terminating through cold
But, centrifuge, dialysing obtains carbon point；
S2, by 180 parts by volume mass fractions be 0.008% HAuCl4Solution is heated to boiling, then adds 6 parts by volume
Mass fraction is 0.8% sodium citrate solution, is stirred at reflux to system and takes on a red color, and is then received through cooling, centrifugation, washing
Meter Jin；
S3, will the 3- sulfydryl -1,2- propane diols of 1 parts by volume and 4500 parts by volume nanogold mix after carry out reaction 7h obtain
To modified nano gold；
S4, the carbon point of 1 parts by volume is mixed with the modified nano gold of 22 parts by volume after carry out reaction 1.3h obtain the use
In the fluorescent optical sensor of detection fluorine ion.
Embodiment 3
A kind of preparation method for being used to detect the fluorescent optical sensor of fluorine ion proposed by the present invention, comprises the following steps：
S1,0.11g 3- amino phenyl boric acids are dissolved in 21g water, utilize 0.5mol/L sodium hydroxide solution regulation system
PH value be 9, then carry out hydro-thermal reaction, wherein, the temperature of hydro-thermal reaction is 150 DEG C, and the time of hydro-thermal reaction is 9.5h, instead
Cooled down after should terminating, centrifugation, the bag filter dialysis 28h for then staying molecular weight to be 800 with carrying obtains carbon point；
S2, by 150ml mass fractions be 0.009% HAuCl4Solution is heated to boiling, then adds 5.8ml mass point
Number is 0.9% sodium citrate solution, is stirred at reflux to system and takes on a red color, and then obtains nanogold through cooling, centrifugation, washing；
S3, will 3uL 3- sulfydryl -1,2- propane diols and 12.6ml nanogold mix after carry out reaction 8h and obtain modification and receive
Meter Jin；
S4,1.5ml carbon point is mixed with 30ml modified nano gold after carry out reaction 0.9h and obtain described being used to detect
The fluorescent optical sensor of fluorine ion.
Embodiment 4
A kind of preparation method for being used to detect the fluorescent optical sensor of fluorine ion that the embodiment of the present invention is proposed, including following step
Suddenly：
S1,0.09g 3- amino phenyl boric acids are dissolved in 19g water, utilize 0.3mol/L potassium hydroxide solution regulation system
PH value be 8, then carry out hydro-thermal reaction, wherein, the temperature of hydro-thermal reaction is 170 DEG C, and the time of hydro-thermal reaction is 8.5h, instead
Cooled down after should terminating, centrifugation, the bag filter dialysis 20h for then staying molecular weight to be 1200 with carrying obtains carbon point；
S2, by 170ml mass fractions be 0.011% HAuCl4Solution is heated to boiling, then adds 5.2ml mass point
Number is 1.1% sodium citrate solution, is stirred at reflux to system and takes on a red color, and then obtains nanogold through cooling, centrifugation, washing；
S3, will 2.5uL 3- sulfydryl -1,2- propane diols and 9.5ml nanogold mix after carry out reaction 12h and obtain modification receiving
Meter Jin；
S4,1ml carbon point is mixed with 18ml modified nano gold after carry out reaction 1.2h and obtain described being used to detect fluorine
The fluorescent optical sensor of ion.
Embodiment 5
A kind of preparation method for being used to detect the fluorescent optical sensor of fluorine ion that the embodiment of the present invention is proposed, including following step
Suddenly：
S1,0.1g 3- amino phenyl boric acids are dissolved in 20g water, utilize 0.1mol/L sodium hydroxide solution regulation system
PH value be 9, then carry out hydro-thermal reaction, wherein, the temperature of hydro-thermal reaction is 160 DEG C, and the time of hydro-thermal reaction is 9h, reaction
Room temperature is cooled to after end, 30min is centrifuged under 10000r/min rotating speed, the bag filter for then staying molecular weight to be 1000 with carrying
Dialysis 24h obtains carbon point；
S2, by 150ml mass fractions be 0.01% HAuCl4Solution is heated to boiling, then adds 5.25ml mass point
Number is 1% sodium citrate solution, is stirred at reflux 15min and is taken on a red color to system, then obtains nanometer through cooling, centrifugation, washing
Gold；
S3, will 5 μ L 3- sulfydryl -1,2- propane diols and 20ml nanogold mix after carry out reaction 10h and obtain modifying nanometer
Gold；
S4,2ml carbon point is mixed with 40ml modified nano golds after carry out reaction 1h and obtain described being used to detect fluorine ion
Fluorescent optical sensor.
Preparation method according to above-described embodiment 1-5, the embodiment of the present invention also proposed one kind and be obtained by embodiment 1-5
To be used for detect the fluorescent optical sensor of fluorine ion.
Fig. 1 is fluorescent quenching figure of the modified nano gold (0-1.33nM) to carbon point of various concentrations in the present invention, in Fig. 1
In, the concentration of modified nano gold is followed successively by 0nM, 0.33nM, 0.67nM, 1nM, 1.33nM from top to bottom, as shown in Figure 1, with
The rise of modified nano gold concentration, the fluorescence intensity of carbon point is gradually quenched.
Fig. 2 is is used to detect fluoride solution (0-117 μ of the fluorescent optical sensor to various concentrations of fluorine ion in the present invention
M fluorescence response figure), in fig. 2, the 1st article of curve from the bottom up is to the 14th article of curve, and fluorinion concentration is respectively 0 μM, 9 μ
M, 18 μM, 27 μM, 36 μM, 45 μM, 54 μM, 63 μM, 72 μM, 81 μM, 90 μM, 99 μM, 108 μM, 117 μM, as shown in Figure 2, with
The increase of fluorinion concentration, the fluorescence intensity of carbon point is also gradually recovered.
Fig. 3 is is used to detect fluoride solution (9-117 μ of the fluorescent optical sensor to various concentrations of fluorine ion in the present invention
M) the linear relationship chart of fluorescence response, linear equation is F-F0=5.30965CF -+ 4.68236, (wherein, F0To add fluorine ion
Front sensor fluorescence intensity level, F for add fluorine ion after sensor fluorescence intensity level, CF-Represent fluorinion concentration,
Unit is μM), the range of linearity is 9-117 μM, and linearly dependent coefficient is 0.9993, and signal to noise ratio, when being 3, test limit is 1.8 μM,
This fluorescent optical sensor shown in the present invention has wider detection range and relatively low test limit to fluorine ion detection, can be used for
Detect fluorine ion.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (21)
1. a kind of preparation method for being used to detect the fluorescent optical sensor of fluorine ion, it is characterised in that comprise the following steps：
It is S1,3- amino phenyl boric acids is soluble in water and pH value of regulation system is 8-10, then carry out hydro-thermal reaction, the hydro-thermal
The temperature of reaction is 145-180 DEG C, and the time of hydro-thermal reaction is 8-10h, and reaction obtains carbon after terminating through cooling, centrifugation, dialysis
Point；
S2, the HAuCl by sodium citrate solution addition boiling4In solution, back flow reaction is then stirred, reaction is passed through after terminating
Cooling, centrifugation, washing obtain the mass fraction of sodium citrate in nanogold, sodium citrate solution for 0.8-1.2%, HAuCl4It is molten
HAuCl in liquid4Mass fraction be 0.008-0.012%, sodium citrate solution and HAuCl4The volume ratio of solution is 5-6:130-
180；
S3, will 3- sulfydryls -1,2-PD and nanogold mix after react obtaining modified nano gold, 3- sulfydryls -1,2- third
The ratio between volume of glycol and nanogold is 1:3500-4500；
S4, carbon point is mixed with modified nano gold after react and obtain the fluorescent optical sensor for being used to detect fluorine ion, carbon
The volume ratio of point and modified nano gold is 1:15-22.
2. it is used for the preparation method for detecting the fluorescent optical sensor of fluorine ion according to claim 1, it is characterised in that in S1
In, 3- amino phenyl boric acids is soluble in water and pH value of regulation system is 8-9.
3. it is used for the preparation method for detecting the fluorescent optical sensor of fluorine ion according to claim 2, it is characterised in that in S1
In, 3- amino phenyl boric acids is soluble in water and pH value of regulation system is 9.
4. being used for the preparation method for detecting the fluorescent optical sensor of fluorine ion according to claim any one of 1-3, its feature exists
In in S1, the temperature of the hydro-thermal reaction is 150-170 DEG C, and the time of hydro-thermal reaction is 8.5-9.5h.
5. it is used for the preparation method for detecting the fluorescent optical sensor of fluorine ion according to claim 4, it is characterised in that in S1
In, the temperature of the hydro-thermal reaction is 160 DEG C, and the time of hydro-thermal reaction is 9h.
6. it is used for the preparation method for detecting the fluorescent optical sensor of fluorine ion, its feature according to any one of claim 1-3
It is, in S1, in dialysis procedure, uses the bag filter dialysis 20-28h for carrying and staying molecular weight for 800-1200.
7. it is used for the preparation method for detecting the fluorescent optical sensor of fluorine ion according to claim 6, it is characterised in that in S1
In, in dialysis procedure, use the bag filter dialysis 22-26h for carrying and staying molecular weight for 900-1100.
8. it is used for the preparation method for detecting the fluorescent optical sensor of fluorine ion according to claim 7, it is characterised in that in S1
In, in dialysis procedure, use carry stay molecular weight be 1000 bag filter dialysis 24h.
9. it is used for the preparation method for detecting the fluorescent optical sensor of fluorine ion, its feature according to any one of claim 1-3
It is, in S2, the mass fraction of sodium citrate is 0.9-1.1%, HAuCl in sodium citrate solution4HAuCl in solution4Matter
Amount fraction is 0.009-0.011%, sodium citrate solution and HAuCl4The volume ratio of solution is 5.2-5.8:150-170.
10. it is used for the preparation method for detecting the fluorescent optical sensor of fluorine ion according to claim 9, it is characterised in that in S2
In, the mass fraction of sodium citrate is 1%, HAuCl in sodium citrate solution4HAuCl in solution4Mass fraction be 0.01%,
Sodium citrate solution and HAuCl4The volume ratio of solution is 5.25:150.
11. it is used for the preparation method for detecting the fluorescent optical sensor of fluorine ion, its feature according to any one of claim 1-3
It is, in S3, the ratio between volume of 3- sulfydryls -1,2-PD and nanogold is 1:3800-4200.
12. it is used for the preparation method for detecting the fluorescent optical sensor of fluorine ion according to claim 11, it is characterised in that in S3
In, the ratio between volume of 3- sulfydryls -1,2-PD and nanogold is 1:4000.
13. it is used for the preparation method for detecting the fluorescent optical sensor of fluorine ion, its feature according to any one of claim 1-3
It is, in S3, the reaction time reacted after 3- sulfydryls -1,2-PD and nanogold mixing is 7-13h.
14. it is used for the preparation method for detecting the fluorescent optical sensor of fluorine ion according to claim 13, it is characterised in that in S3
In, the reaction time reacted after 3- sulfydryls -1,2-PD and nanogold mixing is 8-12h.
15. it is used for the preparation method for detecting the fluorescent optical sensor of fluorine ion according to claim 14, it is characterised in that in S3
In, the reaction time reacted after 3- sulfydryls -1,2-PD and nanogold mixing is 10h.
16. it is used for the preparation method for detecting the fluorescent optical sensor of fluorine ion, its feature according to any one of claim 1-3
It is, in S4, the volume ratio of carbon point and modified nano gold is 1:18-20.
17. it is used for the preparation method for detecting the fluorescent optical sensor of fluorine ion according to claim 16, it is characterised in that in S4
In, the volume ratio of carbon point and modified nano gold is 1:20.
18. it is used for the preparation method for detecting the fluorescent optical sensor of fluorine ion, its feature according to any one of claim 1-3
It is, comprises the following steps：
S1, the 3- amino phenyl boric acids of 0.08-0.12 parts by weight are dissolved in the water of 15-22 parts by weight, the pH value of regulation system is
8-10, then carries out hydro-thermal reaction, wherein, the temperature of hydro-thermal reaction is 145-180 DEG C, and the time of hydro-thermal reaction is 8-10h, instead
After should terminating carbon point is obtained through cooling, centrifugation, dialysis；
S2, by 130-180 parts by volume mass fraction be 0.008-0.012% HAuCl4Solution is heated to boiling, then adds 5-
6 parts by volume mass fractions be 0.8-1.2% sodium citrate solution, be stirred at reflux to system and take on a red color, then through cooling, from
The heart, washing obtain nanogold；
S3, will the 3- sulfydryl -1,2- propane diols of 1 parts by volume and 3500-4500 parts by volume nanogold mix after carry out reaction 7-
13h obtains modified nano gold；
S4, the carbon point of 1 parts by volume is mixed with the modified nano gold of 15-22 parts by volume after carry out reaction 0.8-1.3h and obtain described
Fluorescent optical sensor for detecting fluorine ion.
19. it is used for the preparation method for detecting the fluorescent optical sensor of fluorine ion according to claim 18, it is characterised in that including
Following steps：
S1, the 3- amino phenyl boric acids of 0.09-0.11 parts by weight are dissolved in the water of 19-21 parts by weight, the pH value of regulation system is
8-9, then carries out hydro-thermal reaction, wherein, the temperature of hydro-thermal reaction is 150-170 DEG C, and the time of hydro-thermal reaction is 8.5-9.5h,
Reaction is cooled down after terminating, centrifugation, then stays the bag filter dialysis 20-28h that molecular weight is 800-1200 to obtain carbon point with load；
S2, by 150-170 parts by volume mass fraction be 0.009-0.011% HAuCl4Solution is heated to boiling, then adds
5.2-5.8 parts by volume mass fraction is 0.9-1.1% sodium citrate solution, is stirred at reflux to system and takes on a red color, then through cold
But, centrifuge, washing obtains nanogold；
S3, will the 3- sulfydryl -1,2- propane diols of 1 parts by volume and 3800-4200 parts by volume nanogold mix after carry out reaction 8-
12h obtains modified nano gold；
S4, the carbon point of 1 parts by volume is mixed with the modified nano gold of 18-20 parts by volume after carry out reaction 0.9-1.2h and obtain described
Fluorescent optical sensor for detecting fluorine ion.
20. it is used for the preparation method for detecting the fluorescent optical sensor of fluorine ion according to claim 19, it is characterised in that described
The preparation method of fluorescent optical sensor for detecting fluorine ion comprises the following steps：
S1, the 3- amino phenyl boric acids of 0.1 parts by weight are dissolved in the water of 20 parts by weight, utilize sodium hydroxide solution regulation system
PH value is 9, then carries out hydro-thermal reaction, wherein, the temperature of hydro-thermal reaction is 160 DEG C, and the time of hydro-thermal reaction is 9h, reaction knot
Room temperature is cooled to after beam, 30min is centrifuged under 10000r/min rotating speed, the bag filter for then staying molecular weight to be 1000 with carrying is saturating
Analysis 24h obtains carbon point；
S2, by 150 parts by volume mass fractions be 0.01% HAuCl4Solution is heated to boiling, then adds 5.25 parts by volume matter
The sodium citrate solution that fraction is 1% is measured, 15min is stirred at reflux and is taken on a red color to system, then obtained through cooling, centrifugation, washing
Nanogold；
S3, will the 3- sulfydryl -1,2- propane diols of 1 parts by volume and 4000 parts by volume nanogold mix after carry out reaction 10h obtain
Modified nano gold；
S4, the carbon point of 1 parts by volume is mixed with the modified nano gold of 20 parts by volume after carry out reaction 1h and obtain described being used to detect
The fluorescent optical sensor of fluorine ion.
21. a kind of fluorescent optical sensor for being used to detect fluorine ion, it is characterised in that using such as any one of claim 1-20 institutes
The preparation method for the fluorescent optical sensor for detecting fluorine ion stated is prepared from.
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