CN104655604A - Fluorescence sensor for detecting fluorine ions, and preparation method of fluorescence sensor - Google Patents
Fluorescence sensor for detecting fluorine ions, and preparation method of fluorescence sensor Download PDFInfo
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- CN104655604A CN104655604A CN201510079623.7A CN201510079623A CN104655604A CN 104655604 A CN104655604 A CN 104655604A CN 201510079623 A CN201510079623 A CN 201510079623A CN 104655604 A CN104655604 A CN 104655604A
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Abstract
The invention discloses a fluorescence sensor for detecting fluorine ions, and a preparation method of the fluorescence sensor. The preparation method comprises the steps of dissolving 3-aminophenylboronic acid into water, and adjusting the pH value of the system to be alkaline; then, carrying out a hydrothermal reaction to obtain carbon dots; feeding a sodium citrate solution into a boiling HAuCl4 solution, and carrying out agitation backflow until the system is red; then, cooling, centrifuging and washing to obtain nanogold; mixing 3-sulfydryl-1,2-propylene glycol and the nanogold, and carrying out a reaction to obtain modified nanogold; mixing the carbon dots and the modified nanogold, and carrying out a reaction to obtain the fluorescence sensor for detecting the fluorine ions. According to the preparation method of the fluorescence sensor for detecting the fluorine ions, the process is simple and easy, an environment-friendly effect is achieved, and the preparation method can be generalized into preparation of other luminous nanometer materials; the obtained fluorescence sensor for detecting the fluorine ions can be used for detecting the fluorine ions in a water solution, and is low in toxicity, high in quantum yield as well as good in light stability, biocompatibility and sensitivity.
Description
Technical field
The present invention relates to technical field of analytical chemistry, particularly relate to a kind of for fluorescent optical sensor detecting fluorine ion and preparation method thereof.
Background technology
Fluorine is one of necessary trace element of human body, is the required material maintaining bone and tooth growth.Be more or less the same between the amount meeting the fluorine ion of human body needs and the amount of fluorosis too much caused due to fluorine, the intake grasping fluorine so strict is very important, otherwise easily causes fluorosis.At present, what the detection method of fluorine ion was the most frequently used is spectrophotometric method and fluoride ion selective electrode method.In spectrophotometric method, the polyenergetic of photometer light source, solution is to the existence of the disturbing factors such as the scattering of light, capital makes measurement result depart from Lambert-Beer law, directly affect measuring accuracy, and fluoride ion selective electrode is easily contaminated, zero point and full scale need often to adjust demarcation, working service cost is high, and therefore the application of these two kinds of methods is all subject to restriction to a certain extent.Fluorescent optical sensor have simple to operate, selectivity is high, highly sensitive, instantaneity strong, detects limitation low, signal is intuitively simple, disturbs little, is easy to the advantage distinguished, becomes the study hotspot detecting fluorine ion in recent years.
In in the past twenties years, because nano material has the optics of its uniqueness, electricity and magnetic property, cause the strong interest to building chemical sensor based on nano material, these open one based on the sensor that nano material builds and carry out new era that is simple, sensitive and that detect on the spot to special objective thing.Quantum dot due to have quantum yield high, excite the tunable advantage with emission wavelength, become and detected the most widely used optical nano material such as nucleic acid, enzyme, protein, metallic ion and other Small molecular.But, even if quantum dot also has toxicity when concentration is very low.In addition, quantum dot is dissolved in organic solvent usually, thus greatly limits it in the application analyzing detection field.
Summary of the invention
The present invention proposes a kind of preparation method of the fluorescent optical sensor for detecting fluorine ion, the method process be simple, environmental protection, extend to the preparation of other Illuminant nanometer materials; The invention allows for a kind of fluorescent optical sensor for detecting fluorine ion, it can be used for detecting the fluorine ion in aqueous solution, and toxicity is low, and quantum yield is high, and light stability, biocompatibility and sensitivity are good.
The present invention proposes a kind of preparation method of the fluorescent optical sensor for detecting fluorine ion, comprising the following steps:
S1, be alkalescence by soluble in water for 3-aminobenzene boric acid and the pH value of regulation system, then carry out hydro-thermal reaction, after reaction terminates, obtain carbon point through cooling, centrifugal, dialysis;
S2, sodium citrate solution is added the HAuCl of boiling
4in solution, stirring and refluxing takes on a red color to system, then through cooling, centrifugal, washing obtain nm of gold;
S3, by 3-sulfydryl-1,2-PD and nm of gold mixing after carry out being obtained by reacting modified nano gold;
S4, carbon point is mixed with modified nano gold after be obtained by reacting described in be used for detecting the fluorescent optical sensor of fluorine ion.
Preferably, in S1, by soluble in water for 3-aminobenzene boric acid and the pH value of regulation system is 8-10;
Preferably, in S1, by soluble in water for 3-aminobenzene boric acid and the pH value of regulation system is 8-9;
Preferably, in S1, by soluble in water for 3-aminobenzene boric acid and the pH value of regulation system is 9.
Preferably, in S1, the temperature of described hydro-thermal reaction is 145-180 DEG C, and the time of hydro-thermal reaction is 8-10h;
Preferably, in S1, the temperature of described 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 described hydro-thermal reaction is 160 DEG C, and the time of hydro-thermal reaction is 9h.
Preferably, in S1, in dialysis procedure, adopt carry stay molecular weight be 800-1200 bag filter dialysis 20-28h;
Preferably, in S1, in dialysis procedure, adopt carry stay molecular weight be 900-1100 bag filter dialysis 22-26h;
Preferably, in S1, in dialysis procedure, adopt carry stay molecular weight be 1000 bag filter dialysis 24h.
Preferably, in S2, in sodium citrate solution, the massfraction of sodium citrate is 0.8-1.2%, HAuCl
4hAuCl in solution
4massfraction be 0.008-0.012%, sodium citrate solution and HAuCl
4the volume ratio of solution is 5-6:130-180;
Preferably, in S2, in sodium citrate solution, the massfraction of sodium citrate is 0.9-1.1%, HAuCl
4hAuCl in solution
4massfraction be 0.009-0.011%, sodium citrate solution and HAuCl
4the volume ratio of solution is 5.2-5.8:150-170;
Preferably, in S2, in sodium citrate solution, the massfraction of sodium citrate is 1%, HAuCl
4hAuCl in solution
4massfraction be 0.01%, sodium citrate solution and HAuCl
4the volume ratio of solution is 5.25:150.
Preferably, in S3,3-sulfydryl-1,2-PD is 1:3500-4500 with the ratio of the volume of nm of gold;
Preferably; In S3,3-sulfydryl-1,2-PD is 1:3800-4200 with the ratio of the volume of nm of gold;
Preferably, in S3,3-sulfydryl-1,2-PD is 1:4000 with the ratio of the volume of nm of gold.
Preferably, in S3, the reaction time of carrying out reacting after 3-sulfydryl-1,2-PD and nm of gold mix is 7-13h;
Preferably, in S3, the reaction time of carrying out reacting after 3-sulfydryl-1,2-PD and nm of gold mix is 8-12h;
Preferably, in S3, the reaction time of carrying out reacting after 3-sulfydryl-1,2-PD and nm of gold mix 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, the preparation method of the described fluorescent optical sensor for detecting fluorine ion comprises the following steps:
S1, the 3-aminobenzene boric acid of 0.08-0.12 weight portion is dissolved in the water of 15-22 weight portion, the pH value of regulation system is 8-10, then hydro-thermal reaction is carried out, wherein, the temperature of hydro-thermal reaction is 145-180 DEG C, the time of hydro-thermal reaction is 8-10h, reaction terminate after through cooling, centrifugal, dialysis obtain carbon point;
S2, be the HAuCl of 0.008-0.012% by 130-180 parts by volume massfraction
4solution be heated to boiling, then adding 5-6 parts by volume massfraction is the sodium citrate solution of 0.8-1.2%, and stirring and refluxing takes on a red color to system, then through cooling, centrifugal, washing obtain nm of gold;
S3, obtain modified nano gold by carrying out reaction 7-13h after the mixing of the nm of gold of the 3-of 1 parts by volume sulfydryl-1,2-PD and 3500-4500 parts by volume;
S4, the carbon of 1 parts by volume point is mixed with the modified nano gold of 15-22 parts by volume after carry out reacting 0.8-1.3h obtain described in be used for detecting the fluorescent optical sensor of fluorine ion;
Preferably, the preparation method of the described fluorescent optical sensor for detecting fluorine ion comprises the following steps:
S1, the 3-aminobenzene boric acid of 0.09-0.11 weight portion is dissolved in the water of 19-21 weight portion, the pH value of regulation system is 8-9, then hydro-thermal reaction is carried out, wherein, the temperature of hydro-thermal reaction is 150-170 DEG C, and the time of hydro-thermal reaction is 8.5-9.5h, and reaction terminates rear cooling, centrifugal, then with carry stay molecular weight be 800-1200 bag filter dialysis 20-28h obtain carbon point;
S2, be the HAuCl of 0.009-0.011% by 150-170 parts by volume massfraction
4solution be heated to boiling, then adding 5.2-5.8 parts by volume massfraction is the sodium citrate solution of 0.9-1.1%, and stirring and refluxing takes on a red color to system, then through cooling, centrifugal, washing obtain nm of gold;
S3, obtain modified nano gold by carrying out reaction 8-12h after the mixing of the nm of gold of the 3-of 1 parts by volume sulfydryl-1,2-PD and 3800-4200 parts by volume;
S4, the carbon of 1 parts by volume point is mixed with the modified nano gold of 18-20 parts by volume after carry out reacting 0.9-1.2h obtain described in be used for detecting the fluorescent optical sensor of fluorine ion;
Preferably, the preparation method of the described fluorescent optical sensor for detecting fluorine ion comprises the following steps:
S1, the 3-aminobenzene boric acid of 0.1 weight portion is dissolved in the water of 20 weight portions, the pH value of sodium hydroxide solution regulation system is utilized to be 9, then hydro-thermal reaction is carried out, wherein, the temperature of hydro-thermal reaction is 160 DEG C, and the time of hydro-thermal reaction is 9h, is cooled to room temperature after reaction terminates, centrifugal 30min under the rotating speed of 10000r/min, then with carry stay molecular weight be 1000 bag filter dialysis 24h obtain carbon point;
S2, be the HAuCl of 0.01% by 150 parts by volume massfractions
4solution be heated to boiling, then adding 5.25 parts by volume massfractions is the sodium citrate solution of 1%, and stirring and refluxing 15min takes on a red color to system, then through cooling, centrifugal, washing obtain nm of gold;
S3, obtain modified nano gold by carrying out reaction 10h after the mixing of the nm of gold of the 3-of 1 parts by volume sulfydryl-1,2-PD and 4000 parts by volume;
S4, the carbon of 1 parts by volume point is mixed with the modified nano gold of 20 parts by volume after carry out reacting 1h obtain described in be used for detecting the fluorescent optical sensor of fluorine ion.
The invention allows for a kind of fluorescent optical sensor for detecting fluorine ion, the preparation method for the fluorescent optical sensor detecting fluorine ion described in employing is prepared from.
In the present invention, by selecting 3-aminobenzene boric acid to be raw material, adopt the carbon point of water heat transfer containing boric acid base group, after adding modified nano gold, boric acid base group on carbon point can with the 3-sulfydryl-1 of decorated nanometer gold surface, 2-propylene glycol connects, and carbon point and nm of gold is combined as a whole, thus causes the fluorescence of carbon point by modified nano gold quencher; After adding fluorine ion, fluorine ion and boric acid base group have stronger effect, and the boric acid base group on carbon point and the 3-sulfydryl-1,2-PD on modified nano gold are disconnected, and the fluorescence of carbon point is recovered.
The preparation method of the fluorescent optical sensor for detecting fluorine ion of the present invention, process is simple, environmental protection, can be generalized to the synthesis field of other quantum dots, what obtain has specificity for the fluorescent optical sensor detecting fluorine ion to fluorine ion detection, may be used for the fluorine ion in water pollutions field detection aqueous solution, and toxicity is low, quantum yield is high, light stability and good biocompatibility.
Accompanying drawing explanation
Fig. 1 is that the modified nano gold (0-1.33nM) of variable concentrations in the present invention is to the fluorescent quenching figure of carbon point;
Fig. 2 is for detecting the fluorescent optical sensor of fluorine ion to the fluorescence response figure of the fluoride solution (0-117 μM) of variable concentrations in the present invention;
Fig. 3 is for detecting the fluorescent optical sensor of fluorine ion to the linear relationship chart of fluoride solution (9-117 μM) fluorescence response of variable concentrations in the present invention.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail; should understand; embodiment is only for illustration of the present invention, instead of for limiting the present invention, any amendment, equivalent replacement etc. made on basis of the present invention is all in protection scope of the present invention.
Embodiment 1
The preparation method of a kind of fluorescent optical sensor for detecting fluorine ion that the embodiment of the present invention proposes, comprises the following steps:
S1, be dissolved in the water of 22 weight portions by the 3-aminobenzene boric acid of 0.08 weight portion, the pH value of regulation system is 8, then carries out hydro-thermal reaction, wherein, the temperature of hydro-thermal reaction is 180 DEG C, and the time of hydro-thermal reaction is 8h, reaction terminate after through cooling, centrifugal, dialysis obtain carbon point;
S2, be the HAuCl of 0.012% by 130 parts by volume massfractions
4solution be heated to boiling, then adding 5 parts by volume massfractions is the sodium citrate solution of 1.2%, and stirring and refluxing takes on a red color to system, then through cooling, centrifugal, washing obtain nm of gold;
S3, obtain modified nano gold by carrying out reaction 13h after the mixing of the nm of gold of the 3-of 1 parts by volume sulfydryl-1,2-PD and 3500 parts by volume;
S4, the carbon of 1 parts by volume point is mixed with the modified nano gold of 15 parts by volume after carry out reacting 0.8h obtain described in be used for detecting the fluorescent optical sensor of fluorine ion.
Embodiment 2
The preparation method of a kind of fluorescent optical sensor for detecting fluorine ion that the embodiment of the present invention proposes, comprises the following steps:
S1, be dissolved in the water of 15 weight portions by the 3-aminobenzene boric acid of 0.12 weight portion, the pH value of regulation system is 10, then carries out hydro-thermal reaction, wherein, the temperature of hydro-thermal reaction is 145 DEG C, and the time of hydro-thermal reaction is 10h, reaction terminate after through cooling, centrifugal, dialysis obtain carbon point;
S2, be the HAuCl of 0.008% by 180 parts by volume massfractions
4solution be heated to boiling, then adding 6 parts by volume massfractions is the sodium citrate solution of 0.8%, and stirring and refluxing takes on a red color to system, then through cooling, centrifugal, washing obtain nm of gold;
S3, obtain modified nano gold by carrying out reaction 7h after the mixing of the nm of gold of the 3-of 1 parts by volume sulfydryl-1,2-PD and 4500 parts by volume;
S4, the carbon of 1 parts by volume point is mixed with the modified nano gold of 22 parts by volume after carry out reacting 1.3h obtain described in be used for detecting the fluorescent optical sensor of fluorine ion.
Embodiment 3
The preparation method of a kind of fluorescent optical sensor for detecting fluorine ion that the present invention proposes, comprises the following steps:
S1,0.11g 3-aminobenzene boric acid is dissolved in 21g water, the pH value of the sodium hydroxide solution regulation system of 0.5mol/L is utilized to be 9, then hydro-thermal reaction is carried out, wherein, the temperature of hydro-thermal reaction is 150 DEG C, and the time of hydro-thermal reaction is 9.5h, and reaction terminates rear cooling, centrifugal, then with carry stay molecular weight be 800 bag filter dialysis 28h obtain carbon point;
S2, be the HAuCl of 0.009% by 150ml massfraction
4solution be heated to boiling, then add the sodium citrate solution that 5.8ml massfraction is 0.9%, stirring and refluxing takes on a red color to system, then through cooling, centrifugal, washing obtain nm of gold;
S3, obtain modified nano gold by carrying out reaction 8h after the mixing of the nm of gold of the 3-of 3uL sulfydryl-1,2-PD and 12.6ml;
S4, the carbon of 1.5ml point is mixed with the modified nano gold of 30ml after carry out reacting 0.9h obtain described in be used for detecting the fluorescent optical sensor of fluorine ion.
Embodiment 4
The preparation method of a kind of fluorescent optical sensor for detecting fluorine ion that the embodiment of the present invention proposes, comprises the following steps:
S1,0.09g 3-aminobenzene boric acid is dissolved in 19g water, the pH value of the potassium hydroxide solution regulation system of 0.3mol/L is utilized to be 8, then hydro-thermal reaction is carried out, wherein, the temperature of hydro-thermal reaction is 170 DEG C, and the time of hydro-thermal reaction is 8.5h, and reaction terminates rear cooling, centrifugal, then with carry stay molecular weight be 1200 bag filter dialysis 20h obtain carbon point;
S2, be the HAuCl of 0.011% by 170ml massfraction
4solution be heated to boiling, then add the sodium citrate solution that 5.2ml massfraction is 1.1%, stirring and refluxing takes on a red color to system, then through cooling, centrifugal, washing obtain nm of gold;
S3, carry out reaction 12h obtain modified nano gold by after 2.5uL 3-sulfydryl-1,2-PD and the mixing of 9.5ml nm of gold;
S4, the carbon of 1ml point is mixed with the modified nano gold of 18ml after carry out reacting 1.2h obtain described in be used for detecting the fluorescent optical sensor of fluorine ion.
Embodiment 5
The preparation method of a kind of fluorescent optical sensor for detecting fluorine ion that the embodiment of the present invention proposes, comprises the following steps:
S1,0.1g 3-aminobenzene boric acid is dissolved in 20g water, the pH value of the sodium hydroxide solution regulation system of 0.1mol/L is utilized to be 9, then hydro-thermal reaction is carried out, wherein, the temperature of hydro-thermal reaction is 160 DEG C, and the time of hydro-thermal reaction is 9h, is cooled to room temperature after reaction terminates, centrifugal 30min under the rotating speed of 10000r/min, then with carry stay molecular weight be 1000 bag filter dialysis 24h obtain carbon point;
S2, be the HAuCl of 0.01% by 150ml massfraction
4solution be heated to boiling, then add the sodium citrate solution that 5.25ml massfraction is 1%, stirring and refluxing 15min takes on a red color to system, then through cooling, centrifugal, washing obtain nm of gold;
S3, carry out reaction 10h obtain modified nano gold by after 5 μ L 3-sulfydryl-1,2-PDs and the mixing of 20ml nm of gold;
S4,2ml carbon point is mixed with 40ml modified nano gold after carry out reacting 1h obtain described in be used for detecting the fluorescent optical sensor of fluorine ion.
Preparation method according to above-described embodiment 1-5, the embodiment of the present invention also proposed a kind of fluorescent optical sensor for detecting fluorine ion obtained by embodiment 1-5.
Fig. 1 is that the modified nano gold (0-1.33nM) of variable concentrations in the present invention is to the fluorescent quenching figure of carbon point, in FIG, 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, along with the rising of decorated nanometer gold concentration, the fluorescence intensity quencher gradually of carbon point.
Fig. 2 is for detecting the fluorescent optical sensor of fluorine ion to the fluorescence response figure of the fluoride solution (0-117 μM) of variable concentrations in the present invention, in fig. 2, the 1st article of curve is from the bottom up to the 14th article of curve, fluorinion concentration is respectively 0 μM, 9 μMs, 18 μMs, 27 μMs, 36 μMs, 45 μMs, 54 μMs, 63 μMs, 72 μMs, 81 μMs, 90 μMs, 99 μMs, 108 μMs, 117 μMs, as shown in Figure 2, along with the increase of fluorinion concentration, the fluorescence intensity of carbon point is also recovered gradually.
Fig. 3 is that linear equation is F-F for detecting the fluorescent optical sensor of fluorine ion to the linear relationship chart of fluoride solution (9-117 μM) fluorescence response of variable concentrations in the present invention
0=5.30965C
f -+ 4.68236, (wherein, F
0for adding the fluorescence intensity level of the front sensor of fluorine ion, F be add fluorine ion after the fluorescence intensity level of sensor, C
f-represent fluorinion concentration, unit is μM), the range of linearity is 9-117 μM, linearly dependent coefficient is 0.9993, and signal to noise ratio (S/N ratio) is when being 3, detectability is 1.8 μMs, and this shows that the fluorescent optical sensor in the present invention has wider sensing range and lower detectability to fluorine ion detection, can be used for detecting fluorine ion.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (10)
1. for detecting a preparation method for the fluorescent optical sensor of fluorine ion, it is characterized in that, comprising the following steps:
S1, be alkalescence by soluble in water for 3-aminobenzene boric acid and the pH value of regulation system, then carry out hydro-thermal reaction, after reaction terminates, obtain carbon point through cooling, centrifugal, dialysis;
S2, sodium citrate solution is added the HAuCl of boiling
4in solution, then carry out stirring and refluxing reaction, reaction terminate after through cooling, centrifugal, washing obtain nm of gold;
S3, by 3-sulfydryl-1,2-PD and nm of gold mixing after carry out being obtained by reacting modified nano gold;
S4, carbon point is mixed with modified nano gold after be obtained by reacting described in be used for detecting the fluorescent optical sensor of fluorine ion.
2. according to claim 1 for detecting the preparation method of the fluorescent optical sensor of fluorine ion, it is characterized in that, in S1, by soluble in water for 3-aminobenzene boric acid and the pH value of regulation system is 8-10; Preferably, in S1, by soluble in water for 3-aminobenzene boric acid and the pH value of regulation system is 8-9; Preferably, in S1, by soluble in water for 3-aminobenzene boric acid and the pH value of regulation system is 9.
3. according to claim 1 or 2 for detecting the preparation method of the fluorescent optical sensor of fluorine ion, it is characterized in that, in S1, the temperature of described hydro-thermal reaction is 145-180 DEG C, and the time of hydro-thermal reaction is 8-10h; Preferably, in S1, the temperature of described 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 described hydro-thermal reaction is 160 DEG C, and the time of hydro-thermal reaction is 9h.
4. according to any one of claim 1-3 for detecting the preparation method of the fluorescent optical sensor of fluorine ion, it is characterized in that, in S1, in dialysis procedure, adopt carry stay molecular weight be 800-1200 bag filter dialysis 20-28h; Preferably, in S1, in dialysis procedure, adopt carry stay molecular weight be 900-1100 bag filter dialysis 22-26h; Preferably, in S1, in dialysis procedure, adopt carry stay molecular weight be 1000 bag filter dialysis 24h.
5. according to any one of claim 1-4 for detecting the preparation method of the fluorescent optical sensor of fluorine ion, it is characterized in that, in S2, in sodium citrate solution, the massfraction of sodium citrate is 0.8-1.2%, HAuCl
4hAuCl in solution
4massfraction be 0.008-0.012%, sodium citrate solution and HAuCl
4the volume ratio of solution is 5-6:130-180; Preferably, in S2, in sodium citrate solution, the massfraction of sodium citrate is 0.9-1.1%, HAuCl
4hAuCl in solution
4massfraction be 0.009-0.011%, sodium citrate solution and HAuCl
4the volume ratio of solution is 5.2-5.8:150-170; Preferably, in S2, in sodium citrate solution, the massfraction of sodium citrate is 1%, HAuCl
4hAuCl in solution
4massfraction be 0.01%, sodium citrate solution and HAuCl
4the volume ratio of solution is 5.25:150.
6. according to any one of claim 1-5 for detecting the preparation method of the fluorescent optical sensor of fluorine ion, it is characterized in that, in S3,3-sulfydryl-1,2-PD is 1:3500-4500 with the ratio of the volume of nm of gold; Preferably; In S3,3-sulfydryl-1,2-PD is 1:3800-4200 with the ratio of the volume of nm of gold; Preferably, in S3,3-sulfydryl-1,2-PD is 1:4000 with the ratio of the volume of nm of gold.
7. according to any one of claim 1-6 for detecting the preparation method of the fluorescent optical sensor of fluorine ion, it is characterized in that, in S3, after 3-sulfydryl-1,2-PD and nm of gold mixing, reaction time of carrying out reacting is 7-13h; Preferably, in S3, the reaction time of carrying out reacting after 3-sulfydryl-1,2-PD and nm of gold mix is 8-12h; Preferably, in S3, the reaction time of carrying out reacting after 3-sulfydryl-1,2-PD and nm of gold mix is 10h.
8. according to any one of claim 1-7 for detecting the preparation method of the fluorescent optical sensor of fluorine ion, it is characterized in that, 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.
9. according to any one of claim 1-8 for detecting the preparation method of the fluorescent optical sensor of fluorine ion, it is characterized in that, comprise the following steps:
S1, the 3-aminobenzene boric acid of 0.08-0.12 weight portion is dissolved in the water of 15-22 weight portion, the pH value of regulation system is 8-10, then hydro-thermal reaction is carried out, wherein, the temperature of hydro-thermal reaction is 145-180 DEG C, the time of hydro-thermal reaction is 8-10h, reaction terminate after through cooling, centrifugal, dialysis obtain carbon point;
S2, be the HAuCl of 0.008-0.012% by 130-180 parts by volume massfraction
4solution be heated to boiling, then adding 5-6 parts by volume massfraction is the sodium citrate solution of 0.8-1.2%, and stirring and refluxing takes on a red color to system, then through cooling, centrifugal, washing obtain nm of gold;
S3, obtain modified nano gold by carrying out reaction 7-13h after the mixing of the nm of gold of the 3-of 1 parts by volume sulfydryl-1,2-PD and 3500-4500 parts by volume;
S4, the carbon of 1 parts by volume point is mixed with the modified nano gold of 15-22 parts by volume after carry out reacting 0.8-1.3h obtain described in be used for detecting the fluorescent optical sensor of fluorine ion;
Preferably, the preparation method of the described fluorescent optical sensor for detecting fluorine ion comprises the following steps:
S1, the 3-aminobenzene boric acid of 0.09-0.11 weight portion is dissolved in the water of 19-21 weight portion, the pH value of regulation system is 8-9, then hydro-thermal reaction is carried out, wherein, the temperature of hydro-thermal reaction is 150-170 DEG C, and the time of hydro-thermal reaction is 8.5-9.5h, and reaction terminates rear cooling, centrifugal, then with carry stay molecular weight be 800-1200 bag filter dialysis 20-28h obtain carbon point;
S2, be the HAuCl of 0.009-0.011% by 150-170 parts by volume massfraction
4solution be heated to boiling, then adding 5.2-5.8 parts by volume massfraction is the sodium citrate solution of 0.9-1.1%, and stirring and refluxing takes on a red color to system, then through cooling, centrifugal, washing obtain nm of gold;
S3, obtain modified nano gold by carrying out reaction 8-12h after the mixing of the nm of gold of the 3-of 1 parts by volume sulfydryl-1,2-PD and 3800-4200 parts by volume;
S4, the carbon of 1 parts by volume point is mixed with the modified nano gold of 18-20 parts by volume after carry out reacting 0.9-1.2h obtain described in be used for detecting the fluorescent optical sensor of fluorine ion;
Preferably, the preparation method of the described fluorescent optical sensor for detecting fluorine ion comprises the following steps:
S1, the 3-aminobenzene boric acid of 0.1 weight portion is dissolved in the water of 20 weight portions, the pH value of sodium hydroxide solution regulation system is utilized to be 9, then hydro-thermal reaction is carried out, wherein, the temperature of hydro-thermal reaction is 160 DEG C, and the time of hydro-thermal reaction is 9h, is cooled to room temperature after reaction terminates, centrifugal 30min under the rotating speed of 10000r/min, then with carry stay molecular weight be 1000 bag filter dialysis 24h obtain carbon point;
S2, be the HAuCl of 0.01% by 150 parts by volume massfractions
4solution be heated to boiling, then adding 5.25 parts by volume massfractions is the sodium citrate solution of 1%, and stirring and refluxing 15min takes on a red color to system, then through cooling, centrifugal, washing obtain nm of gold;
S3, obtain modified nano gold by carrying out reaction 10h after the mixing of the nm of gold of the 3-of 1 parts by volume sulfydryl-1,2-PD and 4000 parts by volume;
S4, the carbon of 1 parts by volume point is mixed with the modified nano gold of 20 parts by volume after carry out reacting 1h obtain described in be used for detecting the fluorescent optical sensor of fluorine ion.
10. for detecting a fluorescent optical sensor for fluorine ion, it is characterized in that, adopting and being prepared from for the preparation method of the fluorescent optical sensor detecting fluorine ion as claimed in any one of claims 1-9 wherein.
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| CN201510079623.7A CN104655604B (en) | 2015-02-13 | 2015-02-13 | It is a kind of to be used to detect fluorescent optical sensor of fluorine ion and preparation method thereof |
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| CN105602557A (en) * | 2016-01-14 | 2016-05-25 | 中国科学院理化技术研究所 | Carbon dot with double functionalization of nitrogen-containing and boron-containing functional groups and preparation method thereof |
| CN107794039A (en) * | 2017-10-27 | 2018-03-13 | 江苏大学 | A kind of preparation and its application for being used to detect the boric acid carbon quantum dot of fluorine ion |
| CN113720816A (en) * | 2021-08-16 | 2021-11-30 | 中国水产科学研究院东海水产研究所 | Method for detecting fluorine ions in aquatic product based on silicon dot fluorescence |
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| CN105602557A (en) * | 2016-01-14 | 2016-05-25 | 中国科学院理化技术研究所 | Carbon dot with double functionalization of nitrogen-containing and boron-containing functional groups and preparation method thereof |
| CN107794039A (en) * | 2017-10-27 | 2018-03-13 | 江苏大学 | A kind of preparation and its application for being used to detect the boric acid carbon quantum dot of fluorine ion |
| CN113720816A (en) * | 2021-08-16 | 2021-11-30 | 中国水产科学研究院东海水产研究所 | Method for detecting fluorine ions in aquatic product based on silicon dot fluorescence |
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