CN108051420A - Rare earth coordination compound fluorescent probe and its detection method to total phosphorus in environmental sample - Google Patents
Rare earth coordination compound fluorescent probe and its detection method to total phosphorus in environmental sample Download PDFInfo
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- CN108051420A CN108051420A CN201810036052.2A CN201810036052A CN108051420A CN 108051420 A CN108051420 A CN 108051420A CN 201810036052 A CN201810036052 A CN 201810036052A CN 108051420 A CN108051420 A CN 108051420A
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- 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
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- 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"
- G01N2021/6432—Quenching
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Abstract
The invention discloses a kind of rare earth coordination compound fluorescent probe and its detection methods to total phosphorus in environmental sample, belong to environmental monitoring technology field.The fluorescence probe is by Ciprofloxacin and Eu3+The complex formed in the solution system of pH=6.5~8.5.After orthophosphates adds in the solution system containing the complex, originally by Eu3+The fluorescence for the Ciprofloxacin being quenched completely obtains the recovery of part, and the higher recovery extent of orthophosphates concentration is also accordingly promoted.In certain scope, the fluorescence intensity of phosphate concentration and Ciprofloxacin is in good linear relationship, available for accurate detection phosphate concentration.
Description
Technical field
The present invention relates to the detection methods of total phosphorus in water sample and Atmospheric particulates, and in particular to a kind of rare earth compounding fluorescence
Probe and its detection method to total phosphorus in environmental sample, belong to environmental monitoring technology field.
Background technology
Phosphorus may exist in the form of element phosphor, orthophosphates, pyrophosphate, metaphosphate and organophosphor etc. in water.It is led
Want the phosphate buider of source used in sanitary sewage, chemical fertilizer, organophosphorus pesticide and modern age detergent etc..Phosphorus in water body is
A kind of key element that algal grown needs, excessive phosphorus is to cause water body filth foreign odor, makes lake that eutrophication and bay occur
There is the main reason for red tide.Total phosphorus is that the phosphorus of various forms is transformed into the knot measured after orthophosphates by water sample after resolution
Fruit is measured with the phosphorous milligram number of every liter of water sample.
The method for measuring water sample total phosphorus at present has：Ammonium molybdate spectrophotometric method, concentration limit are 0.01 mg/L；
Flow injection-ammonium molybdate spectrophotometric method, detection are limited to 0.005mg/L.The side of ion-chromatographic determination soluble phosphate
Method detection is limited to 0.007mg/L.The assay method of water sample total phosphorus at present, sensitivity is totally not high enough, and it is total to meet water body reluctantly
The demand that phosphorus measures, and spectrophotometry also there are problems that Matrix effects coexist.
The content of the invention
It is an object of the invention to solve, water sample total phosphorus determination sensitivity in the prior art is not high and presence coexists matrix and does
The problem of disturbing, and a kind of rare earth coordination compound fluorescent probe and its detection method to total phosphorus in environmental sample are provided.
Specific technical solution of the present invention is as follows：
A kind of rare earth coordination compound fluorescent probe, for orthophosphates content in determination sample, which is by ring third
Sha Xing and Eu3+The complex formed in the solution system of pH=6.5~8.5.
After orthophosphates adds in the solution system containing the complex, originally by Eu3+The Ciprofloxacin being quenched completely
Fluorescence obtains the recovery of part, and the higher recovery extent of orthophosphates concentration is also accordingly promoted.In certain scope, phosphate radical
Concentration and the fluorescence intensity of Ciprofloxacin are in good linear relationship, available for accurate detection phosphate concentration.
Preferably, in the solution system, Eu3+Molar concentration rate with Ciprofloxacin is (3~1):1.
In another arrangement, formed in the solution system of the complex and also contain neopelex, is i.e. the fluorescence
Probe is by Ciprofloxacin, Eu3+The complex formed with neopelex in the solution system of pH=6.5~8.5.Ten
The effect of dialkyl benzene sulfonic acids sodium is enhancing Eu3+Formation with Ciprofloxacin complex is so as to improving detection sensitivity.
Preferably, in the solution system, Eu3+, Ciprofloxacin and neopelex molar concentration rate be
(3~1)：1：(5~75).
Another object of the present invention is to provide a kind of rare earth coordination compound fluorescent probe to orthophosphates content in sample
Detection method, concrete scheme include two kinds：
Scheme one is：It is (3~1) by molar ratio:1 Ciprofloxacin and Eu3+The buffering for being dissolved in pH=6.5~8.5 is molten
In liquid system, mixing is stood to form coordination compound fluorescent probe after, add in the sample containing orthophosphates, mixing constant volume；It then will be mixed
It closes solution and is placed under excitation wavelength and irradiate, the fluorescence intensity of solution is measured then at transmitted wave strong point；Finally changed according to standard curve
Calculation obtains orthophosphates content in sample.
Scheme two is：It is (3~1) by molar ratio：1：The Eu of (5~75)3+, Ciprofloxacin and neopelex it is molten
Solution in the buffer solution system of pH=6.5~8.5, mixing is stood to form coordination compound fluorescent probe after, add in containing orthophosphates
Sample, mixing constant volume；Then mixed solution is placed under excitation wavelength and irradiated, the fluorescence of solution is measured then at transmitted wave strong point
Intensity；Finally convert to obtain orthophosphates content in sample according to standard curve.
Wherein, scheme two adds neopelex compared with scheme one in solution system is detected, can be with
The sensitivity of detection is improved, specific effect will be explained by following embodiment.
In above two detection scheme, excitation wavelength can be 310~350nm, launch wavelength can be 380~
450nm.Under the wave band, fluorescence intensity is higher, can improve detection sensitivity.
In above two detection scheme, buffer solution system can be amion acetic acid buffer solution.Certainly, buffer solution body
The effect of system is to control the pH of detection architecture, therefore other will not be similarly suitable to buffer solution that measure interferes
With not as restriction.
In above two detection scheme, original sample to be tested can be phosphorous water sample or aerosol sample, example
TSP the and PM2.5 particulate matters such as gathered from air.But in two kinds of detection schemes, the P form that can be detected is the positive phosphorus of dissolubility
Hydrochlorate, therefore the sample for adding in detection architecture is the sample containing orthophosphates.When total phosphorus in sample to be detected or other
During non-solubility phosphate content, sample must be cleared up in advance, be translated into dissolubility orthophosphates.
When sample to be tested is phosphorous water sample, phosphorous water sample first passes through resolution pretreatment in advance, and then quantitative digestion solution is determined
Hold as the sample containing orthophosphates.
When sample to be tested is phosphorous particulate matter, phosphorous particulate matter is cleared up in acid solution in advance, then quantitative
Digestion solution constant volume is taken as the sample containing orthophosphates.
The rare earth coordination compound fluorescent probe of the present invention, which measures orthophosphates, has high sensitivity, the detection limit of method
Up to 4.6nM can be used in trace orthophosphates Concentration Testing.
Description of the drawings
Fig. 1 is the fluorescence spectrum under different disposal in embodiment 1；Wherein：(a) fluorescence spectrum of Ciprofloxacin (CIP),
(b)10.0μmol·L-1The fluorescence spectrum of Ciprofloxacin (CIP), (c) CIP-Eu in the presence of phosphate radical3+The fluorescence light of complex
Spectrum, (d) 10.0 μm of olL-1CIP-Eu in the presence of phosphate radical3+The fluorescence spectrum of complex；
Fig. 2 is the fluorescence spectrum under different disposal in embodiment 2；Wherein：(a) fluorescence spectrum of Ciprofloxacin (CIP),
(b)CIP-Eu3+The fluorescence spectrum of complex, (c) 10.0 μm of olL-1CIP-Eu in the presence of phosphate radical3+The fluorescence light of complex
Spectrum；
Fig. 3 is the fluorescence spectrum under different disposal in embodiment 3；Wherein：(a) fluorescence spectrum of Ciprofloxacin (CIP),
(b)CIP-Eu3+The fluorescence spectrum of complex, (c) 10.0 μm of olL-1CIP-Eu in the presence of phosphate radical3+The fluorescence light of complex
Spectrum；
Fig. 4 is the fluorescence spectrum under different disposal in embodiment 4；Wherein：(a) fluorescence spectrum of Ciprofloxacin (CIP),
(b)CIP-Eu3+The fluorescence spectrum of complex, (c) 10.0 μm of olL-1CIP-Eu in the presence of phosphate radical3+The fluorescence light of complex
Spectrum；
Fig. 5 is the fluorescence spectrum under different disposal in embodiment 5；Wherein：(a) fluorescence spectrum of Ciprofloxacin (CIP),
(b)CIP-Eu3+The fluorescence spectrum of complex, (c) 10.0 μm of olL-1CIP-Eu in the presence of phosphate radical3+The fluorescence light of complex
Spectrum；
Fig. 6 is the fluorescence spectrum under different disposal in embodiment 6；Wherein：(a) fluorescence spectrum of Ciprofloxacin (CIP),
(b)CIP-Eu3+The fluorescence spectrum of complex, (c) 10.0 μm of olL-1CIP-Eu in the presence of phosphate radical3+The fluorescence light of complex
Spectrum；
Fig. 7 is the fluorescence spectrum under different phosphate concentrations；Wherein, the curve of the top represents 4.0 μM of phosphate concentrations
Under fluorescence spectrum, the corresponding phosphate concentration of curve of lower section successively decreases successively, and the curve of bottom represents 0.05 μM of phosphate radical
Fluorescence spectrum under concentration；
Fig. 8 is the zwitterion and influence of the fulvic acid to detection coexisted in water sample.
Specific embodiment
The present invention is further elaborated and illustrated with reference to the accompanying drawings and detailed description.The method of the present invention both may be used
For directly detecting the orthophosphates being directly present in sample, total phosphorus can also will be measured after Specimen eliminating, principle is
Consistent.Below by taking the latter as an example, illustrate the specific implementation process and effect of the present invention.
In the present invention, the rare earth ion coordination compound fluorescent probe based on Resonance energy transfer is sensitive, selective enumeration method environment
The analysis method of total phosphorus, excellent realization method comprise the following steps in sample (in water sample and Atmospheric particulates)：
(1) pre-process：
The pretreatment of water sample：Acquisition water sample 25mL is taken to add in 3mL concentrated nitric acid sum number grain zeolites in 50mL conical flasks, shake
Heating is concentrated into 10mL on electric hot plate after even, if water sample is still muddy, adds 2 mL concentrated nitric acids and continues to heat, until water
Until sample becomes clear, continue to heat water sample to closely doing, the high-purity water dissolution residues of 10mL are added in after cooling, are used in combination
1.0mol/L NaOH solutions water transfer sample pH is then transferred in 25mL colorimetric cylinders to neutrality, quarter is settled to high purity water
Degree.
The pretreatment of atmospheric aerosol samples：TSP the and PM2.5 particulate matters of acquisition are transferred to two 50mL cones respectively
In shape bottle, several zeolites are respectively added in, are then respectively adding 10mL high purity waters, 1mL concentrated nitric acids are added after shaking up, in heating plate
Upper heating is boiled near dry, adds the high-purity water dissolution residues of 7mL after cooling, and with the NaOH solution water transfer of 1.0mol/L
Sample pH is then transferred in 10mL colorimetric cylinders to neutrality, scale is settled to high purity water.
(2) test experience method：In 10.0mL colorimetric cylinders, a certain amount of following solution is sequentially added：Amion acetic acid delays
Rush solution, Ciprofloxacin (CIP) solution, Eu (NO3)3Solution, neopelex solution (SDBS) are stood after mixing
10min.A certain amount of sodium radio-phosphate,P-32 solution (or sample to be tested) is added, then dilution is settled to 10.0mL, and above-mentioned solution is most
It is final concentration of：5.0×10-2Mol/L amion acetic acids buffer solution (pH=6.5~8.5), Eu (NO in buffer system3)3With ring third
Husky star molar concentration rate is 3:1~1:1 (ciprofloxacin solution concentration is 10 μM), neopelex solution (SDBS) rubs
Your concentration is 0.5~7.5 × 10-4mol/L.10min is put in room temperature decentralization after mixing, in 310~350nm of excitation wavelength, transmitted wave
The fluorescence intensity of solution is measured at long 380~450nm.Optimum optimization experiment condition is：5.0×10-2Mol/L amion acetic acids delay
Rush solution (pH=7.5), Eu (NO3)3Solution is 1.5 with ciprofloxacin solution concentration ratio:1 (ciprofloxacin solution concentration be 10 μ
), M neopelex solution (SDBS) is 1.0 × 10-4Mol/L, after mixing room temperature decentralization put 10min, in excitation wavelength
The fluorescence intensity of solution is measured at 330nm, launch wavelength 415nm.
(3) drafting of standard working curve：7 10.0mL colorimetric cylinders are taken, it is parallel to sequentially add following solution：500μ
L1.0mol/L amion acetic acids buffer solution (pH=7.5), 100 μ L1.0 × 10-3Mol/L Ciprofloxacins, 30 μ L5.0 × 10- 3mol/L Eu3+,100μL 1.0×10-2Mol/L SDBS stand 10min after mixing.Be separately added into 0 in 7 colorimetric cylinders again,
50th, then the certain density phosphoric acid sodium standard solutions of 100,200,300,400,500 μ L dilute and are settled to 10.0mL, after mixing
10min is placed at room temperature, and the fluorescence intensity of solution is measured at excitation wavelength 330nm, launch wavelength 415nm.By measuring solution
Fluorescence intensity and the corresponding phosphate concentration added in draw standard working curve.
(4) sample concentration measures：By the water sample or aerosol sample of pretreatment, empirically step (2) measures accordingly
Corresponding phosphate concentration, then root is calculated by the standard working curve that (3) obtain in the fluorescence intensity measured by fluorescence intensity
Sample actual concentrations are calculated according to the extension rate in sample pre-treatments or continuous mode.
Embodiment 1
In the present embodiment, 5.0 × 10-2In mol/L amion acetic acids buffer solution (pH=7.5), Eu (NO are added in3)3It is molten
Liquid, ciprofloxacin solution and neopelex solution (SDBS), it is 10 μ to keep Ciprofloxacin solution concentration in mixed liquor
M, Eu3+Concentration is 15 μM, and neopelex solution (SDBS) concentration is 1.0 × 10-4mol/L.Mixed solution is stood
After 10min, Ciprofloxacin-Eu is formed3+Complex.Sodium radio-phosphate,P-32 solution is added in the mixed solution, keeps phosphate radical in solution
Concentration is 10 μM, and mixed liquor is placed under 330nm excitation wavelengths and is irradiated, you can is detected under launch wavelength (most preferably 415nm)
The fluorescence intensity of solution.
In order to show in the present embodiment, the effect of the principle and each component of fluorescence probe played in system is also distinguished
To Ciprofloxacin (CIP), add in the Ciprofloxacin of phosphate radical and Ciprofloxacin-Eu3+Complex is under identical excitation wavelength
Fluorescence spectrum is determined.Fluorescence spectrum shown in the result is shown in Figure 1, it can be seen from the figure that in Eu3+Situation about being not present
Under, 10 μM of Ciprofloxacin (CIP) has stronger fluorescence intensity (Fig. 1 .a) at 415nm, and add in 10 μM of phosphate radicals it
Afterwards, Ciprofloxacin fluorescence intensity has almost no change (Fig. 1 .b), as the Eu for adding in 15 μM3+Afterwards, the fluorescence peak of Ciprofloxacin is several
It is quenched completely, and Eu3+Characteristic fluorescence at ion 615nm is significantly enhanced (Fig. 1 .c), this is because Eu3+Addition shape
Into Ciprofloxacin-Eu3+Ciprofloxacin has occurred to Eu in complex3+Energy transfer between ion, so that Ciprofloxacin
The fluorescence intensity of itself substantially reduces, and enhances Eu3+Characteristic fluorescence.When to Ciprofloxacin-Eu3+Add in complexes system
After entering 10 μM of phosphate radicals, it can be found that the fluorescence of Ciprofloxacin obtains the recovery of part, and Eu3+Characteristic fluorescence apparent drop again
Low (Fig. 1 .d), this may be due to Eu3+It can be combined with phosphate radical, so as to weaken Ciprofloxacin to Eu3+Energy between ion
Amount transfer, enables the fluorescence part of Ciprofloxacin to recover.This fluorescent quenching and fluorescence recovery process can shine in ultraviolet lamp
Penetrate lower carry out naked eye.
Under the experiment condition of the present embodiment, Ciprofloxacin-Eu3+The relation of complexes system and phosphate concentration such as Fig. 7,
With the increase of phosphate concentration, the fluorescence intensity of complexes system Ciprofloxacin in itself is gradually recovered, at 0.05~4.0 μM
In concentration range, the fluorescence intensity of phosphate concentration and Ciprofloxacin is in good linear relationship (F-F0)/F0=0.116c+
0.0273, R2=0.994, the detection limit of method shows that the sensitivity of method is very high, the method than having reported at present up to 4.6nM
It is apparent high.
Embodiment 2
In the present embodiment, 5.0 × 10-2In mol/L amion acetic acids buffer solution (pH=6.5), Eu (NO are added in3)3It is molten
Liquid, ciprofloxacin solution and neopelex solution (SDBS), it is 10 μ to keep Ciprofloxacin solution concentration in mixed liquor
M, Eu3+Concentration is 30 μM, and neopelex solution (SDBS) concentration is 0.5 × 10-4mol/L.Mixed solution is stood
After 10min, Ciprofloxacin-Eu is formed3+Complex.Sodium radio-phosphate,P-32 solution is added in the mixed solution, keeps phosphate radical in solution
Concentration is 10 μM, and mixed liquor is placed under 310nm excitation wavelengths and is irradiated, you can the fluorescence for detecting solution at the emission wavelength is strong
Degree.In the solution system, CIP-Eu in the presence of phosphate radical3+The fluorescence spectrum of complex is as shown in Fig. 2 .c, and individually ring third
For husky star fluorescence spectrum as shown in Fig. 2 .a, which adds in the CIP-Eu before phosphate radical3+Complex fluorescent spectrum is as schemed
Shown in 2.b.
0.75 μM is limited to using the detection of detection architecture detection phosphate radical in the present embodiment.
Embodiment 3
In the present embodiment, 5.0 × 10-2In mol/L amion acetic acids buffer solution (pH=8.5), Eu (NO are added in3)3It is molten
Liquid, ciprofloxacin solution and neopelex solution (SDBS), it is 10 μ to keep Ciprofloxacin solution concentration in mixed liquor
M, Eu3+Concentration is 10 μM, and neopelex solution (SDBS) concentration is 7.5 × 10-4mol/L.Mixed solution is stood
After 10min, Ciprofloxacin-Eu is formed3+Complex.Sodium radio-phosphate,P-32 solution is added in the mixed solution, keeps phosphate radical in solution
Concentration is 10 μM, and mixed liquor is placed under 310nm excitation wavelengths and is irradiated, you can the fluorescence for detecting solution at the emission wavelength is strong
Degree.In the solution system, CIP-Eu in the presence of phosphate radical3+The fluorescence spectrum of complex is as shown in Fig. 3 .c, and individually ring third
For husky star fluorescence spectrum as shown in Fig. 3 .a, which adds in the CIP-Eu before phosphate radical3+Complex fluorescent spectrum is as schemed
Shown in 3.b.
0.5 μM is limited to using the detection of detection architecture detection phosphate radical in the present embodiment.
Embodiment 4
In the present embodiment, 5.0 × 10-2In mol/L amion acetic acids buffer solution (pH=6.5), Eu (NO are added in3)3It is molten
Liquid, ciprofloxacin solution and neopelex solution (SDBS), it is 10 μ to keep Ciprofloxacin solution concentration in mixed liquor
M, Eu3+Concentration is 10 μM, and neopelex solution (SDBS) concentration is 7.5 × 10-4mol/L.Mixed solution is stood
After 10min, Ciprofloxacin-Eu is formed3+Complex.Sodium radio-phosphate,P-32 solution is added in the mixed solution, keeps phosphate radical in solution
Concentration is 10 μM, and mixed liquor is placed under 350nm excitation wavelengths and is irradiated, you can the fluorescence for detecting solution at the emission wavelength is strong
Degree.In the solution system, CIP-Eu in the presence of phosphate radical3+The fluorescence spectrum of complex is as shown in Fig. 4 .c, and individually ring third
For husky star fluorescence spectrum as shown in Fig. 4 .a, which adds in the CIP-Eu before phosphate radical3+Complex fluorescent spectrum is as schemed
Shown in 4.b.
0.25 μM is limited to using the detection of detection architecture detection phosphate radical in the present embodiment.
Embodiment 5
In the present embodiment, 5.0 × 10-2In mol/L amion acetic acids buffer solution (pH=8.5), Eu (NO are added in3)3It is molten
Liquid, ciprofloxacin solution and neopelex solution (SDBS), it is 10 μ to keep Ciprofloxacin solution concentration in mixed liquor
M, Eu3+Concentration is 30 μM, and neopelex solution (SDBS) concentration is 0.5 × 10-4mol/L.Mixed solution is stood
After 10min, Ciprofloxacin-Eu is formed3+Complex.Sodium radio-phosphate,P-32 solution is added in the mixed solution, keeps phosphate radical in solution
Concentration is 10 μM, and mixed liquor is placed under 350nm excitation wavelengths and is irradiated, you can the fluorescence for detecting solution at the emission wavelength is strong
Degree.In the solution system, CIP-Eu in the presence of phosphate radical3+The fluorescence spectrum of complex is as shown in Fig. 5 .c, and individually ring third
For husky star fluorescence spectrum as shown in Fig. 5 .a, which adds in the CIP-Eu before phosphate radical3+Complex fluorescent spectrum is as schemed
Shown in 5.b.
1.0 μM are limited to using the detection of detection architecture detection phosphate radical in the present embodiment.
Embodiment 6
In the present embodiment, 5.0 × 10-2In mol/L amion acetic acids buffer solution (pH=7.5), Eu (NO are added in3)3It is molten
Liquid and ciprofloxacin solution, it is 10 μM to keep Ciprofloxacin solution concentration in mixed liquor, Eu3+Concentration is 15 μM.Mixed solution is quiet
After putting 10min, Ciprofloxacin-Eu is formed3+Complex.Sodium radio-phosphate,P-32 solution is added in the mixed solution, keeps phosphoric acid in solution
Root concentration is 10 μM, and mixed liquor is placed under 330nm excitation wavelengths and is irradiated, you can is examined under launch wavelength (most preferably 415nm)
Survey the fluorescence intensity of solution.
In the solution system, CIP-Eu in the presence of phosphate radical3+The fluorescence spectrum of complex is and independent as shown in Fig. 6 .c
Ciprofloxacin fluorescence spectrum as shown in Fig. 6 .a, the solution system add in phosphate radical before CIP-Eu3+Complex fluorescent light
Spectrum is as shown in Fig. 6 .b.
0.25 μM is limited to using the detection of detection architecture detection phosphate radical in the present embodiment.Compared with Example 1, this implementation
It is decreased obviously in example without addition neopelex solution, overall sensitivity.
Embodiment 7
The present embodiment is used to verify the method choice of detection architecture in embodiment 1.
Under experiment parameter in embodiment 1, test phosphate radical with it is other can compatible zwitterion and water sample
In a large amount of existing fulvic acids to the disturbed condition of system of determination fluorescence intensity.During experiment, keep different zwitterions or
The molar ratio of fulvic acid and phosphate radical is 1:1 (molar concentration is 8.0 μM), the results are shown in Figure 8, except Cr3+It is slightly dry
Disturb it is outer, it is other can compatible zwitterion and fulvic acid nearly all not interference measurement, show that this method has good selection
Property.
Embodiment 8
The present embodiment is used to verify the method accuracy of detection architecture in embodiment 1.Based on rare earth ion complex fluorescent
The analysis method of total phosphorus is as follows in probe in detecting water sample：
(1) pretreatment of water sample：Acquisition water sample 25mL is taken to add in 3mL concentrated nitric acid sum number grain zeolites in 50mL conical flasks,
Heating is concentrated into 10mL on electric hot plate after shaking up, and if water sample is still muddy, adds 2mL concentrated nitric acids and continues to heat, until
Until water sample becomes clear, continue to heat water sample to closely doing, the high-purity water dissolution residues of 10mL are added in after cooling, are used in combination
1.0mol/L NaOH solutions water transfer sample pH is then transferred in 25mL colorimetric cylinders to neutrality, quarter is settled to high purity water
Degree.
(2) experimental procedure：In 10.0mL colorimetric cylinders, following solution is sequentially added：500 μ L 1.0mol/L amion acetic acids
Buffer solution (pH=7.5), 100 μ L 1.0 × 10-3Mol/L Ciprofloxacins, 30 μ L 5.0 × 10-3 mol/L Eu3+,100μL
1.0×10-2Mol/L SDBS stand 10min after mixing.A certain amount of sample to be tested is added, then dilution is settled to
10.0mL, after mixing room temperature decentralization put 10min, the fluorescence of measure solution is strong excitation wavelength 330nm, launch wavelength 415nm at
Degree.
(3) drafting of standard working curve：7 10.0mL colorimetric cylinders are taken, it is parallel to sequentially add following solution：500μL
1.0mol/L amion acetic acids buffer solution (pH=7.5), 100 μ L 1.0 × 10-3Mol/L Ciprofloxacins, 30 μ L 5.0 × 10- 3mol/L Eu3+,100μL 1.0×10-2Mol/L SDBS stand 10min after mixing.Be separately added into 0 in 7 colorimetric cylinders again,
50th, then the certain density phosphoric acid sodium standard solutions of 100,200,300,400,500 μ L dilute and are settled to 10.0mL, after mixing
10min is placed at room temperature, and the fluorescence intensity of solution is measured at excitation wavelength 330nm, launch wavelength 415nm.By measuring solution
Fluorescence intensity and the corresponding phosphate concentration added in draw standard working curve.
(4) sample concentration measures：By the water sample or atmospheric sample of pretreatment, empirically step (2) measures corresponding glimmering
Corresponding phosphate radical is calculated by the standard working curve that experimental procedure (3) obtains in the fluorescence intensity measured by luminous intensity
Concentration calculates the actual concentrations of sample further according to the extension rate in sample pre-treatments or continuous mode.
By said determination method with the P-Mo blue spectrophotometry of national standard respectively to total in identical lake water and wastewater sample
Phosphorus concentration is measured, and testing result is as shown in table 1, and as seen from the table, two methods measurement result is basically identical.
1 water sample Method Measuring Total Quantity of Phosphorus of table compares
Actual sample measures application：Surface water, sewage sample and atmospheric aerosol samples are applied the inventive method to survey
It is fixed.The pretreatment of water sample is as described above.The pretreatment of atmospheric aerosol samples is as follows：By TSP the and PM2.5 particulate matters of acquisition
It is transferred to respectively in two 50mL conical flasks, respectively adds in several zeolites, be then respectively adding 10mL high purity waters, added after shaking up
1mL concentrated nitric acids, on hot plate heating are boiled near and done, add the high-purity water dissolution residues of 7mL after cooling, be used in combination
The NaOH solution water transfer sample pH of 1.0mol/L is then transferred in 10mL colorimetric cylinders to neutrality, quarter is settled to high purity water
Degree.
The total phosphorus determination result of each water sample and Atmospheric particulates is as shown in table 2, table 3.
2 actual water sample total phosphorus determination of table
3 Atmospheric particulates total phosphorus determination of table
Embodiment described above is a kind of preferable scheme of the present invention, and so it is not intended to limiting the invention.Have
The those of ordinary skill of technical field is closed, without departing from the spirit and scope of the present invention, various changes can also be made
Change and modification.For example, in above-described embodiment, using amion acetic acid buffer solution, but in fact the buffer solution only plays surely
The effect of pH is determined, as long as using the buffer solution without interference with measure；In above-described embodiment, using detergent alkylate first
Acid sodium solution, but in fact the surfactant only rises and has sensitization to measure system, as long as using without interference with measure
Other surfactants also may be used.The pretreatment of sample is needed depending on actually detected purpose, can carry out carrying out.
Therefore the technical solution that all modes for taking equivalent substitution or equivalent transformation are obtained, all falls in protection scope of the present invention.
Claims (10)
1. a kind of rare earth coordination compound fluorescent probe, for orthophosphates content in determination sample, which is characterized in that the fluorescence probe
It is by Ciprofloxacin and Eu3+The complex formed in the solution system of pH=6.5~8.5.
2. rare earth coordination compound fluorescent probe as described in claim 1, which is characterized in that formed in the solution system of the complex
Also contain neopelex.
3. rare earth coordination compound fluorescent probe as described in claim 1, which is characterized in that in the solution system, Eu3+With ring
The molar concentration rate of third husky star is (3~1):1.
4. rare earth coordination compound fluorescent probe as claimed in claim 2, which is characterized in that in the solution system, Eu3+, ring
The molar concentration rate of third husky star and neopelex is (3~1)：1：(5~75).
5. a kind of rare earth coordination compound fluorescent probe is to the detection method of orthophosphates content in sample, it is characterised in that：General mole
Than for (3~1):1 Eu3+It is dissolved in Ciprofloxacin in the buffer solution system of pH=6.5~8.5, mixing, which stands to be formed, matches somebody with somebody
After closing object fluorescence probe, the sample containing orthophosphates, mixing constant volume are added in；Then mixed solution is placed under excitation wavelength and shone
It penetrates, the fluorescence intensity of solution is measured then at transmitted wave strong point；It finally converts to obtain orthophosphates in sample according to standard curve to contain
Amount.
6. a kind of rare earth coordination compound fluorescent probe is to the detection method of orthophosphates content in sample, it is characterised in that：General mole
Than for (3~1)：1：The Eu of (5~75)3+, Ciprofloxacin and neopelex be dissolved in the bufferings of pH=6.5~8.5
In solution system, mixing is stood to form coordination compound fluorescent probe after, add in the sample containing orthophosphates, mixing constant volume；Then will
Mixed solution, which is placed under excitation wavelength, to be irradiated, and the fluorescence intensity of solution is measured then at transmitted wave strong point；Finally according to standard curve
Conversion obtains orthophosphates content in sample.
7. rare earth coordination compound fluorescent probe is to the detection method of orthophosphates content in sample, spy as described in claim 5 or 6
Sign is：The excitation wavelength is 310~350nm, and the launch wavelength is 380~450nm.
8. rare earth coordination compound fluorescent probe is to the detection method of orthophosphates content in sample, spy as described in claim 5 or 6
Sign is：The buffer solution system is amion acetic acid buffer solution.
9. rare earth coordination compound fluorescent probe is to the detection method of orthophosphates content in sample, spy as described in claim 5 or 6
Sign is：Sample to be tested is phosphorous water sample, and phosphorous water sample first passes through resolution pretreatment, then quantitative digestion solution constant volume conduct in advance
The sample containing orthophosphates.
10. rare earth coordination compound fluorescent probe is to the detection method of orthophosphates content in sample as described in claim 5 or 6,
It is characterized in that：Sample to be tested is phosphorous particulate matter, and phosphorous particulate matter is cleared up in acid solution, then quantitatively cancelled in advance
Liquid constant volume is solved as the sample containing orthophosphates.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110132911A (en) * | 2019-04-15 | 2019-08-16 | 浙江大学 | Total phosphorus detection method in water sample based on compound ratio fluorescent probe |
| CN111234246A (en) * | 2020-01-15 | 2020-06-05 | 浙江大学 | Double-emission-ratio fluorescent probe based on rare earth ion framework material and detection method |
| CN111521594A (en) * | 2020-05-13 | 2020-08-11 | 重庆工程职业技术学院 | Novel nano-composite, preparation method thereof and application thereof in sewage detection |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030054949A1 (en) * | 2001-05-23 | 2003-03-20 | Chang Eddie L. | Immobilized metalchelate complexes for catalysis and decontamination of pesticides and chemical warfare nerve-agents |
| CN101709326A (en) * | 2009-11-05 | 2010-05-19 | 浙江大学 | DNA measuring method of rare earth coordination compound fluorescent probe |
| CN105255484A (en) * | 2015-10-16 | 2016-01-20 | 合肥学院 | Preparation method of SrAlB2O7:Eu<3+> fluorescent probe for detection of OPs (organophosphorus pesticides) |
| CN105884806A (en) * | 2016-06-21 | 2016-08-24 | 福州大学 | Preparation method of fluorescent probe and oxytetracycline detection method based on same |
-
2018
- 2018-01-15 CN CN201810036052.2A patent/CN108051420B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030054949A1 (en) * | 2001-05-23 | 2003-03-20 | Chang Eddie L. | Immobilized metalchelate complexes for catalysis and decontamination of pesticides and chemical warfare nerve-agents |
| CN101709326A (en) * | 2009-11-05 | 2010-05-19 | 浙江大学 | DNA measuring method of rare earth coordination compound fluorescent probe |
| CN105255484A (en) * | 2015-10-16 | 2016-01-20 | 合肥学院 | Preparation method of SrAlB2O7:Eu<3+> fluorescent probe for detection of OPs (organophosphorus pesticides) |
| CN105884806A (en) * | 2016-06-21 | 2016-08-24 | 福州大学 | Preparation method of fluorescent probe and oxytetracycline detection method based on same |
Non-Patent Citations (1)
| Title |
|---|
| 舒苗等: "稀土E u3+荧光探针法测定饮用水中那氟沙星的含量", 《理化检验 化学分册》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110132911A (en) * | 2019-04-15 | 2019-08-16 | 浙江大学 | Total phosphorus detection method in water sample based on compound ratio fluorescent probe |
| CN110132911B (en) * | 2019-04-15 | 2020-03-17 | 浙江大学 | Method for detecting total phosphorus in water sample based on compound ratiometric fluorescent probe |
| CN111234246A (en) * | 2020-01-15 | 2020-06-05 | 浙江大学 | Double-emission-ratio fluorescent probe based on rare earth ion framework material and detection method |
| CN111521594A (en) * | 2020-05-13 | 2020-08-11 | 重庆工程职业技术学院 | Novel nano-composite, preparation method thereof and application thereof in sewage detection |
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