CN104359888A - Lanthanide metal europium ion complex probe-based method for detecting pH value - Google Patents
Lanthanide metal europium ion complex probe-based method for detecting pH value Download PDFInfo
- Publication number
- CN104359888A CN104359888A CN201410699276.3A CN201410699276A CN104359888A CN 104359888 A CN104359888 A CN 104359888A CN 201410699276 A CN201410699276 A CN 201410699276A CN 104359888 A CN104359888 A CN 104359888A
- Authority
- CN
- China
- Prior art keywords
- value
- europium ion
- ion complex
- lanthanide series
- series metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a lanthanide metal europium ion complex probe-based method for detecting a pH value. The detection method mainly comprises the following steps: firstly, carrying out fluorescence intensity scanning on a to-be-detected sample A including lanthanide metal europium ion complexes and solutions with different pH values; observing the change of the fluorescence intensity, and carrying out quantitative detection on the pH values of the solutions, so as to obtain a linear interval between the pH values and the fluorescence intensity; and detecting the fluorescence intensity of a to-be-detected sample B including the lanthanide metal europium ion complexes and a to-be-detected water body sample, so as to obtain the pH value of the to-be-detected water body sample. The method disclosed by the invention is capable of achieving the detection effect of a traditional method, and has good selectivity, high response speed, short detection time, simplicity of operation and low price; a time-resolved fluorescence signal is strong and stable; and the repeatability of an experimental method and the recognizable degree of the fluorescence signal in a complicated environment are ensured, so that the ultimate practicability of the detection method is powerfully guaranteed.
Description
Technical field
The invention belongs to chemical analysis technology field, be specifically related to a kind of pH value detection method based on lanthanide series metal europium ion Complex probe.
Background technology
PH value, i.e. potential of hydrogen are the important indicators of water quality.The pH value of natural water is many between 6 ~ 9; Potable water pH requires between 6.5 ~ 8.5; The pH value of some process water should ensure between 7.0 ~ 8.5, otherwise will have corrosive attack to hardware and pipeline.PH value and acidity, basicity are not only had any different but also be related.The power of what pH value represented the is Acidity of Aikalinity of water, and acidity and basicity are the content of contained acid or alkaloid substance in water.The change of the pH value in water quality is predictive of the degree of water pollutions.Whether in breeding water body, pH value reflects the change of water quality very intuitively, the vigor of such as algae and the existence etc. of carbon dioxide, can be inferred in normal range by the size of pH value and daily variation.
The meaning measuring pH value is that it indicates the base attribute of water; When there is ANOMALOUS VARIATIONS, indicate pollution; Acidulous water can promote dissolving metal, is corrosive to metal, thus likely causes metal acute and chronic poisoning; Alkaline water can promote the precipitation of metal, affects the sensory properties of water, and has corrosive attack, and on water correction, pH value affects coagulation and chlorination effect.China and most countries Drinking Water water quality standard specify that the scope of pH value is 6.5 ~ 8.5.It is generally acknowledged that the pH value of potable water (6.5 ~ 9.5) in a big way can not affect health and life is drunk.
Except traditional colourimetry and pH meter method, in the research detected pH value at present, the research based on fluorometry is in the majority.Mainly contain three kinds of different types in based on the method for fluorescence analysis, the first kind is that mensuration two kinds of different dyes are to the ratio of the fluorescence intensity that pH value responds, namely usually said Ratio-type pH sensor, Equations of The Second Kind is the fluorescence lifetime measuring dyestuff, and the 3rd class is the fluorescence intensity directly measuring dyestuff.First kind method, i.e. Ratio-type pH sensor, the problem such as can be good at solving in sensor the dye leakage that usually runs into and background signal is high, but how to find two kinds to have the dyestuff of different response effect to pH value, and can be applied in pH sensor, be a very large difficult problem.Equations of The Second Kind method, studied pH value by the fluorescence lifetime measuring dyestuff, the advantage of this kind of method is that fluorescence lifetime does not depend on fluorescence intensity and wavelength etc., has relative independentability, and therefore its interference is less.But this method needs high-grade, precision and advanced and complicated instrument and equipment, because which limit its application in pH detection.So in fact, the 3rd class methods, namely directly measure the fluorescence intensity of dyestuff, be answer method with the most use at present.But this method is normally used is have short-life dyestuff, thus detecting the interference being easily subject to the fluorescence of detection system own and biosome endogenous fluorescence in application, makes the background signal of detection method higher, affecting the signal to noise ratio (S/N ratio) of detection method.Therefore, presently, the detection method developing pH value in a kind of quick, easy, stability and specific environment water is necessary.
Summary of the invention
The problem such as to be easily disturbed, unstable and background signal is strong in order to the detection signal existed can be effectively reduced during in environment water pH value detects, and improve detection signal can identification and stability, the object of the present invention is to provide a kind of pH value detection method based on lanthanide series metal europium ion Complex probe.By the inventive method, achieve simple, quick, the stable and specific detection of damping fluid and actual environment water body sample pH value.
For achieving the above object, the present invention adopts following technical scheme:
Based on a pH value detection method for lanthanide series metal europium ion Complex probe, comprise the following steps successively:
(1) lanthanide series metal europium ion complex is synthesized;
(2) storing solution of lanthanide series metal europium ion complex is prepared;
(3) solution of different pH value is prepared;
(4) preparation comprises the testing sample A of lanthanide series metal europium ion complex and different pH value;
(5) testing sample A fluorescence spectrophotometer is carried out to the scanning of fluorescence intensity, observe the change of fluorescence intensity, realize the quantitative detection to solution ph, obtain between the linear zone between pH value and fluorescence intensity;
(6) water body sample to be measured is prepared;
(7) preparation comprises the testing sample B of lanthanide series metal europium ion complex and water body sample to be measured;
(8) testing sample B fluorescence spectrophotometer is carried out to the scanning of fluorescence intensity, between the linear zone obtain the fluorescence intensity obtained contrast step (5), obtain the pH value of water body sample to be measured.
Preferably, the concrete steps of described step (1) are as follows: by 88mg Eu
2o
3heating for dissolving, in 2.0mL concentrated hydrochloric acid, after adding the unnecessary concentrated hydrochloric acid of heat abstraction, adds ethanol dilution and obtains clear solution, i.e. EuCl
3ethanolic solution; Another 20mL ethanol dissolves 337mg TTA (thenoyltrifluoroacetone), by EuCl
3ethanolic solution and the ethanolic solution of TTA join in there-necked flask, heating water bath, magnetic agitation, control temperature is 60 DEG C, is 6.0 by NaOH solution adjust ph, control temperature and pH value, after reaction 40min, separately dissolves 5-NH with 15mL ethanol
2-phen, then drops in reaction system, and now controlling temperature of reaction is 58 DEG C, and continue reaction 5h, after completion of the reaction, hold over night in refrigerator, has yellow solid to separate out, suction filtration; With ethanol and milli-Q water, vacuum drying at 50 DEG C, then with ethyl alcohol recrystallization 2 times, the yellow solid obtaining having long-life phosphors performance is described lanthanide series metal europium ion complex Eu (TTA)
3(5-NH
2-phen), represent with ETN.
Preferred, described 5-NH
2-phen is obtained by following method: with phen (1,10-phenanthroline) for raw material obtains 5-NO by nitration reaction
2-phen, then obtains described 5-NH by reduction reaction
2-phen.
More preferred, described nitration reaction is that the reaction time is 45min, and temperature of reaction is 165 DEG C with the concentrated sulphuric acid and red fuming nitric acid (RFNA) acid mixture for nitrating agent; Described reduction reaction be with containing palladium massfraction be the palladium carbon of 5% for catalyzer, hydrazine hydrate is reductive agent, and the reaction time is 5.0h, and temperature of reaction is 90 ~ 92 DEG C.
Preferably, the storing solution preparation of the lanthanide series metal europium ion complex described in step (2): accurately take the ETN pressed powder that 5.065mg step (1) is obtained, be dissolved in 100mL volumetric flask with ethanol, obtaining concentration is 5 × 10
-5molL
-1the storing solution of lanthanide series metal europium ion complex.
Preferably, the preparation of the different pH value described in step (3): pH value is formed by B – R buffer 1.98 ~ 11.98 time, other pH value is regulated by HCl and NaOH solution and forms;
Described B – R damping fluid is 0.04molL by concentration
-1phosphoric acid, boric acid and acetic acid acid mixture, use 0.2molL
-1naOH is adjusted to required pH value and forms; Other pH value solution described is by 2.0molL
-1hCl and 2.0molL
-1naOH regulates and forms.
Preferred, the pH value of described different pH value is respectively 0,0.5,1.0,1.5,1.98,2.5,2.87,3.5,4.1,4.5,5.02,5.5,6.09,6.5,7.0,7.5,7.96,8.5,8.95,9.5,9.91,10.5,10.88,11.5,11.98,12.5,13.0,13.5 and 14.0.
Preferably, the step of the preparation of the testing sample A described in step (4) is: prepare in a series of 10mL color comparison tube, add the storing solution of the obtained lanthanide series metal europium ion complex of 1.0mL step (2) respectively, put into 60 DEG C of baking ovens and remove alcohol solvent, the solution constant volume of the different pH value then using step (3) to prepare respectively is to scale.
Preferably, the described detection to solution ph of step (5) is specially: record with the change of the time-resolved fluorescence intensity of the obtained testing sample solution of fluorescence spectrophotometer determination step (4), maximum excitation wavelength and maximum emission wavelength are respectively 355nm and 611nm, time delay is 0.1ms, exciting slit and launching slit is 5.0nm, thus the quantitative detection realized testing sample solution ph, obtain between the linear zone between pH value and fluorescence intensity.
Preferred, be respectively between the linear zone of described pH value and fluorescence intensity: pH 1.5 ~ 7.5,10 ~ 14.
Preferably, the described water body sample to be measured of step (6) is: sewage, river, spring, lake water or tap water sample.Wherein spring and tap water sample do not do pre-service, and sewage, river and lake water sample first filter, then at the upper visible suspension of centrifugal segregation of supercentrifuge (12000rpm/min, 5min).
Preferably, preparation steps and the step (4) of the testing sample B described in step (7) are similar, just different pH value in step (4) is changed to water body water sample to be measured, be specially: prepare a series of 10mL color comparison tube, add the storing solution of the obtained lanthanide series metal europium ion complex of 1.0mL step (2) respectively, put into 60 DEG C of baking ovens and remove alcohol solvent, the water body sample constant volume to be measured then using step (6) to prepare respectively is to scale; The scanning step of the described fluorescence intensity to testing sample B of step (8) is similar with step (5), the condition of scanning is identical, before difference is actual scanning, first makes pre-detection with the pH size of guestimate sample with wide pH value test paper.
Principle of the present invention is: because the endogenous fluorescence etc. in the background fluorescence of detection system itself and biosome is all short-life fluorescence signal, if the material with long-life phosphors characteristic can be utilized as dyestuff, service time resolved fluorescence mode, remove or reduce the interference of short-life background fluorescence signal, so will have huge raising to the specificity of detection method and practical application.Find the advantages such as lanthanide series metal europium ion complex not only has that fluorescence lifetime is long, fluorescence quantum yield is high and fluorescence signal is stable under study for action, and when pH value changes, its time-resolved fluorescence intensity has the response of rapid sensitive.Therefore, the present invention utilizes long-term durability luminous lanthanide series metal europium ion complex to propose the detection method of pH value in a kind of easy, quick, stable and specific environment water.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) detection method is simple, to pH value response rapidly;
(2) high specificity, other organism and inorganics etc. of existing in solution do not affect testing result;
(3) cheap, only need use the lanthanide series metal of method synthesis simply and easily europium ion complex;
(4) simple operation, without the need to the Sample pretreatment of complexity;
(5) pH value that can be applicable in actual environment water body detects;
(6) time-resolved fluorescence signal is strong and stable, ensure that the repeatability of experimental technique and fluorescence signal in complex environment can identification, make the practical application of detection method obtain strong guarantee.
The inventive method, compared with classic method, not only can reach the Detection results of classic method, and has good selectivity; Simultaneously, the inventive method fast response time, detection time are short, easy and simple to handle and cheap, the more important thing is the long-term durability luminous character that the inventive method utilizes lanthanide series metal europium ion complex and has, operate time resolved fluorometric analytic approach, effectively reduce or eliminate the interference of background fluorescence signal, improve intensity and the stability of detection signal, detection method use is in actual applications obtained and effectively ensures.
Accompanying drawing explanation
Fig. 1 is lanthanide series metal europium ion complex Eu (TTA) used in the present invention
3(5-NH
2-phen) structural formula.
Fig. 2 is lanthanide series metal europium ion complex Eu (TTA) used in the present invention
3(5-NH
2-phen) synthesis step.
Fig. 3 be in the present invention dissolved oxygen DO and ionic strength to the interference figure of detection method.
Fig. 4 is the time-resolved fluorescence utilizing emitted light spectrogram that in the present invention, different pH value detects.
Fig. 5 is curve map and the range of linearity figure of detection method in the present invention.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Below instrument and equipment used in the part embodiment of the present invention, other not marked experiment condition conveniently or the condition of advising with its manufacturer: Perkin-Elmer LS-55 phosphorescence spectrophotometer (Britain); Centrifuge 5417R small desk high speed freezing centrifuge (German Eppendorf company); Merck Millipore ultrapure water machine (Germany); PHS-3B type pH meter (Shanghai Precision Scientific Apparatus Co., Ltd); Electronic balance TE124S (German Sartorius company).
Embodiment 1
With thenoyltrifluoroacetone (TTA), the lanthanide series metal europium ion complex that 1,10-phenanthroline (phen) is part: Eu (TTA)
3(5-NH
2-phen) preparation, concrete steps are as follows:
A. with the 5-NH that 1,10-phenanthroline (phen) is raw material
2the synthesis of-phen
Synthesis step: the nitration of (1) phen.In 250mL there-necked flask, add the 13mL concentrated sulphuric acid, under magnetic agitation condition, add 2.0g phen in batches, magnetic agitation is dissolved, and slowly heats up, when temperature is raised to 150 DEG C, slowly add 5.5mL red fuming nitric acid (RFNA), temperature of reaction controls at 165 DEG C, continues reaction 45min.After completion of the reaction, reactant liquor is carefully poured in 130g mixture of ice and water, after trash ice melts completely, use 2.0molL
-1naOH solution adjust ph is 7.0, now has a large amount of yellow mercury oxide to generate, decompress filter, and washing, air-dryly in air obtains crude product NO
2-phen, with ethyl alcohol recrystallization 2 times, obtain yellow crystals, 60 DEG C of vacuum dryings, are NO
2-phen.(2) NO
2-phen is reduced to NH
2-phen.In 250mL there-necked flask, add 30mL ethanol, then add 1.6g NO
2-phen, heating for dissolving under stirring condition, then adds 0.5g Pd/C, and is warmed up to reflux state, continues to stir 10min, is then dropwised with the hydrazine hydrate/ethanolic solution of 1:1 proportioning by 10mL in 60min, keeps reflux state 5.0h.Decompress filter while hot after completion of the reaction, obtains orange-red solution; Being distilled by this solution has a large amount of yellow mercury oxide to generate, then hold over night in refrigerator, suction filtration, and dry, ethyl alcohol recrystallization 2 times, at 60 DEG C, vacuum drying obtains crystal.
B. lanthanide series metal europium ion complex Eu (TTA)
3(5-NH
2-phen) synthesis
Synthesis step: take 88mg Eu
2o
3heating for dissolving, in 2.0mL concentrated hydrochloric acid, after adding the unnecessary concentrated hydrochloric acid of heat abstraction, adds ethanol and dilutes to obtain clear solution, be i.e. EuCl
3ethanolic solution.Separately dissolve 337mg TTA with 20mL ethanol.By EuCl
3ethanolic solution and the ethanolic solution of TTA slowly join in there-necked flask, heating water bath, magnetic agitation, control temperature is 60 DEG C, uses 2.0molL
-1naOH solution adjust ph is 6.0, control temperature and pH value, reaction 40min.After 40min, separately dissolve 5-NH with 15mL ethanol
2-phen, then drops in reaction system, and now controlling temperature of reaction is 58 DEG C of continuation reaction 5h, and after completion of the reaction, hold over night in refrigerator, has yellow solid to separate out, suction filtration.With ethanol and milli-Q water, vacuum drying at 50 DEG C, then with ethyl alcohol recrystallization 2 times, obtain the yellow solid with long-life phosphors performance---Eu (TTA)
3(5-NH
2-phen), represent with ETN, its structural formula is as shown in Figure 1.Above-mentioned synthesis step as shown in Figure 2.
The stability study of embodiment 2:ETN time-resolved fluorescence intensity
Get 10 different 10mL color comparison tubes, add the storing solution of 1.0mL ETN respectively, put into 60 DEG C of baking ovens and remove alcohol solvent.Be that the B – R damping fluid constant volume of 7.5 is to scale by pH value subsequently, abundant dissolving mixes, left at room temperature 10min, after ETN fully dissolves and stablizes, successively getting 3.0mL solution joins in 1-cm cuvette, and record with the change of its time-resolved fluorescence intensity of Perkin-Elmer LS-55 phosphorescence spectrophotometric determination, maximum excitation wavelength and maximum emission wavelength are respectively 355nm and 611nm, slit is 5.0nm, and time delay is 0.1ms.Thus obtain 10 different time-resolved fluorescence intensity levels, carry out relative standard deviation calculating to it, relative standard deviation is 3.2%, is less than 5%, and result illustrates that the method has good stability.
Embodiment 3: dissolved oxygen DO and ionic strength affect research
A. dissolved oxygen DO is to the influence research of ETN time-resolved fluorescence intensity
The present embodiment has prepared the solution of 3 kinds of different dissolved oxygens, i.e. oxygen saturation solution, nitrification solution and saturation of the air solution.The pH value of 3 kinds of solution controls 7.0.Then measure the time-resolved fluorescence intensity of ETN in these 3 kinds of solution according to the step method of embodiment 2, thus its impact is studied.Outcome record is in the A figure of accompanying drawing 3.The time-resolved fluorescence intensity that result shows the ETN in 3 kinds of solution is substantially constant, thus absolutely proves that the interference of the oxygen concentration in solution to detection method is negligible, can not consider that dissolved oxygen DO is on impact of the present invention in reality detects.
B. ionic strength is to the influence research of ETN time-resolved fluorescence intensity
The NaCl solution that the present embodiment has prepared 19 kinds of variable concentrations (is respectively 0.01,0.02,0.04,0.06,0.08,0.1,0.12,0.14,0.16,0.18,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9 and 1.0molL
-1), then study its impact on the time-resolved fluorescence intensity of ETN.Control the pH value of these 19 kinds of solution 6.5.Then measure the time-resolved fluorescence intensity of ETN in these 19 kinds of solution according to the step method of embodiment 2, thus its impact is studied.Outcome record is in the B figure of accompanying drawing 3.The time-resolved fluorescence intensity that result shows the ETN in 19 kinds of solution is substantially constant, thus absolutely proves in solution lower than 1.0molL
-1the interference of ionic strength to detection method negligible, reality detect in can not consider that ionic strength is on impact of the present invention.
Embodiment 4: the detect delay of different pH value
In order to the method for analysis verification the present invention proposition is to the response of different pH value, the present embodiment has prepared the B – R damping fluid of pH value from 1.98 to 11.98 and has regulated other pH value of pH with HCl and NaOH that (pH value is respectively 0,0.5,1.0,1.5,12.5,13.0,13.5 and 14.0) solution.Then, get the storing solution of 1.0mL ETN respectively, join in 28 different 10mL color comparison tubes, put into 60 DEG C of baking ovens and remove alcohol solvent.Subsequently respectively with the solution constant volume of different pH value to scale, abundant dissolving mixes, left at room temperature 10min, after ETN fully dissolves and stablizes, successively getting 3.0mL solution respectively from low to high according to pH value joins in 1-cm cuvette, record by its time-resolved fluorescence intensity of Perkin-Elmer LS-55 phosphorescence spectrophotometric determination, maximum excitation wavelength and maximum emission wavelength are respectively 355nm and 611nm, exciting slit and launching slit is 5.0nm, time delay is 0.1ms, thus obtain 28 different time-resolved fluorescence intensity levels, outcome record in figure 4.As can be seen from the A figure of accompanying drawing 4, pH value and time-resolved fluorescence intensity have obvious corresponding relation, and time-resolved fluorescence intensity level raises along with the rising of pH, and when pH is between 7.5 to 9.5, time-resolved fluorescence intensity reaches maximal value.As can be seen from the B figure of accompanying drawing 4, after pH value is more than 9.5, along with the lasting rising of pH value, time-resolved fluorescence intensity significantly reduces.As can be seen from the figure, the method is rapid for the response of pH value, and signal stabilization, signal to noise ratio (S/N ratio) is high.
Embodiment 5: the linear analysis of detection method
The relation of pH value and time-resolved fluorescence intensity is as shown in the A figure of accompanying drawing 5.As can be seen from the A figure of accompanying drawing 5, this curve is divided into four parts, and Part I is pH 0 ~ 1.5, and now time-resolved fluorescence intensity is almost close to 0, shows with this understanding, and the time-resolved fluorescence intensity of ETN is almost by complete cancellation; Part II is pH 1.5 ~ 7.5, this stage, the time-resolved fluorescence intensity of ETN also significantly raised along with the rising of pH value, and within the scope of this, time-resolved fluorescence intensity and pH value present good linear relationship, and linear equation and related coefficient are as shown in the B figure of accompanying drawing 5; Part III is pH 7.5 ~ 9.5, and now the time-resolved fluorescence intensity of ETN reaches maximal value; Part IV is pH 9.5 ~ 14, when pH is greater than 9.5, the time-resolved fluorescence intensity of ETN reduces along with the rising of pH value, when pH value is between 10 to 14, time-resolved fluorescence intensity and pH value present good linear relationship, and linear equation and related coefficient are as shown in the B figure of accompanying drawing 5.
Embodiment 6: Evaluation on specificity
In order to explore specificity of the present invention, the present embodiment have selected a series of organism and inorganics chaff interference carries out specificity research to the method in the present invention.In this experiment, pH controls 7.0.Outcome record in Table 1.As can be seen from Table 1, listed a series of organism and the existence of inorganics can be ignored substantially on the impact of the detect delay of pH value, and the absolute value of relative standard deviation, between 0.07% ~ 2.77%, is less than 5%.So the detection method that the present invention proposes has good antijamming capability, ensure that its applied research in actual environment water sample.
Table 1 Evaluation on specificity experimental result
Embodiment 7: the detect delay of actual environment water body sample pH value
In order to verify the practical application of the method that the present invention proposes, being employed herein 5 kinds of different actual environment water sample samples, being respectively sewage, river, spring, lake water and tap water sample.Wherein spring and tap water sample do not do pre-service, and sewage, river and lake water sample first filter, then at the upper visible suspension of centrifugal segregation of supercentrifuge (12000rpm/min, 5min).Before reality detects, first make pre-detection with wide pH value test paper, the pH of testing result display sewage is greater than 9, and other water samples pH is all less than 8.Then by the step method in embodiment 2 and 4, pH value detection has been carried out to these 5 kinds of environment water samples, and carried out comparative study by by the result measured by the testing result of method of the present invention and pH meter.Outcome record in table 2.As can be seen from Table 2, the testing result of method of the present invention's proposition and the result measured by pH meter have good consistance.Result absolutely proves, the detection method that the present invention proposes has good practical application.
Table 2 actual environment water body testing result contrasts
| Sample | pH a | pH b | Deviation |
| Sewage | 10.87 | 10.79 | 0.08 |
| River | 6.81 | 6.79 | 0.02 |
| Spring | 6.99 | 6.92 | 0.07 |
| Lake water | 7.05 | 6.98 | 0.07 |
| Tap water | 6.80 | 6.77 | 0.03 |
In table 2, pH
arepresent the result utilizing the present invention to record; PH
brepresent the result that pH meter records
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. based on a pH value detection method for lanthanide series metal europium ion Complex probe, it is characterized in that, comprise the following steps successively:
(1) lanthanide series metal europium ion complex is synthesized;
(2) storing solution of lanthanide series metal europium ion complex is prepared;
(3) solution of different pH value is prepared;
(4) preparation comprises the testing sample A of lanthanide series metal europium ion complex and different pH value;
(5) testing sample A fluorescence spectrophotometer is carried out to the scanning of fluorescence intensity, observe the change of fluorescence intensity, realize the quantitative detection to solution ph, obtain between the linear zone between pH value and fluorescence intensity;
(6) water body sample to be measured is prepared;
(7) preparation comprises the testing sample B of lanthanide series metal europium ion complex and water body sample to be measured;
(8) testing sample B fluorescence spectrophotometer is carried out to the scanning of fluorescence intensity, between the linear zone obtain the fluorescence intensity obtained contrast step (5), obtain the pH value of water body sample to be measured.
2. the pH value detection method based on lanthanide series metal europium ion Complex probe according to claim 1, is characterized in that, the concrete steps of step (1) described synthesis lanthanide series metal europium ion complex are as follows: by 88mg Eu
2o
3heating for dissolving, in 2.0mL concentrated hydrochloric acid, after adding the unnecessary concentrated hydrochloric acid of heat abstraction, adds ethanol dilution and obtains clear solution, i.e. EuCl
3ethanolic solution; Another 20mL ethanol dissolves 337mg TTA, by EuCl
3ethanolic solution and the ethanolic solution of TTA join in there-necked flask, heating water bath, magnetic agitation, control temperature is 60 DEG C, is 6.0 by NaOH solution adjust ph, control temperature and pH value, after reaction 40min, separately dissolves 5-NH with 15mL ethanol
2drop to after-phen in reaction system, now controlling temperature of reaction is 58 DEG C, and continue reaction 5h, after completion of the reaction, hold over night in refrigerator, has yellow solid to separate out, suction filtration; With ethanol and milli-Q water, vacuum drying at 50 DEG C, then with ethyl alcohol recrystallization 2 times, the yellow solid obtained is described lanthanide series metal europium ion complex.
3. the pH value detection method based on lanthanide series metal europium ion Complex probe according to claim 2, is characterized in that, described 5-NH
2-phen is obtained by following method: be that raw material obtains 5-NO by nitration reaction with phen
2-phen, then obtains described 5-NH by reduction reaction
2-phen;
Described nitration reaction is that the reaction time is 45min, and temperature of reaction is 165 DEG C with the acid mixture of the concentrated sulphuric acid and red fuming nitric acid (RFNA) for nitrating agent; Described reduction reaction be with containing palladium massfraction be the palladium carbon of 5% for catalyzer, hydrazine hydrate is reductive agent, and the reaction time is 5.0h, and temperature of reaction is 90 ~ 92 DEG C.
4. the pH value detection method based on lanthanide series metal europium ion Complex probe according to claim 1, it is characterized in that, the storing solution preparation steps of the lanthanide series metal europium ion complex described in step (2) is: take the lanthanide series metal europium ion complex that 5.065mg step (1) is obtained, be dissolved in 100mL volumetric flask with ethanol, obtaining concentration is 5 × 10
-5molL
-1the storing solution of lanthanide series metal europium ion complex.
5. the pH value detection method based on lanthanide series metal europium ion Complex probe according to claim 1, it is characterized in that, the preparation steps of the different pH value described in step (3) is: pH value is formed by B – R buffer 1.98 ~ 11.98 time, and other pH value is regulated by HCl and NaOH solution and forms;
Described B – R damping fluid is 0.04molL by concentration
-1phosphoric acid, boric acid and acetic acid acid mixture, use 0.2molL
-1naOH is adjusted to required pH value and forms; Other pH value solution described is by 2.0molL
-1hCl and 2.0molL
-1naOH regulates and forms.
6. the pH value detection method based on lanthanide series metal europium ion Complex probe according to claim 5, it is characterized in that, the pH value of described different pH value is respectively 0,0.5,1.0,1.5,1.98,2.5,2.87,3.5,4.1,4.5,5.02,5.5,6.09,6.5,7.0,7.5,7.96,8.5,8.95,9.5,9.91,10.5,10.88,11.5,11.98,12.5,13.0,13.5 and 14.0.
7. the pH value detection method based on lanthanide series metal europium ion Complex probe according to claim 1, it is characterized in that, the step of the preparation of the testing sample A described in step (4) is: prepare a series of 10mL color comparison tube, add the storing solution of the obtained lanthanide series metal europium ion complex of 1.0mL step (2) respectively, put into 60 DEG C of baking ovens and remove alcohol solvent, the solution constant volume of the different pH value then using step (3) to prepare respectively is to scale.
8. the pH value detection method based on lanthanide series metal europium ion Complex probe according to claim 1, it is characterized in that, the described fluorescence intensity condition of scanning of step (5) is: maximum excitation wavelength and maximum emission wavelength are respectively 355nm and 611nm, time delay is 0.1ms, and exciting slit and launching slit is 5.0nm; Be respectively between described pH value and the linear zone of fluorescence intensity: pH 1.5 ~ 7.5,10 ~ 14.
9. the pH value detection method based on lanthanide series metal europium ion Complex probe according to claim 1, is characterized in that, the water body sample to be measured described in step (6) is sewage, river, spring, lake water or tap water sample.
10. the pH value detection method based on lanthanide series metal europium ion Complex probe according to claim 1, it is characterized in that, the preparation steps of the testing sample B described in step (7) is: prepare a series of 10mL color comparison tube, add the storing solution of the obtained lanthanide series metal europium ion complex of 1.0mL step (2) respectively, put into 60 DEG C of baking ovens and remove alcohol solvent, the water body sample constant volume to be measured then using step (6) to prepare respectively is to scale; The scanning step of the described fluorescence intensity to testing sample B of step (8) is: first make pre-detection with guestimate pH size with wide pH value test paper, then scan according to the described fluorescence intensity condition of scanning of step (5).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410699276.3A CN104359888B (en) | 2014-11-26 | 2014-11-26 | A kind of pH value detection method based on lanthanide series metal europium ion Complex probe |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410699276.3A CN104359888B (en) | 2014-11-26 | 2014-11-26 | A kind of pH value detection method based on lanthanide series metal europium ion Complex probe |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104359888A true CN104359888A (en) | 2015-02-18 |
| CN104359888B CN104359888B (en) | 2019-04-05 |
Family
ID=52527170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410699276.3A Expired - Fee Related CN104359888B (en) | 2014-11-26 | 2014-11-26 | A kind of pH value detection method based on lanthanide series metal europium ion Complex probe |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104359888B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106432306A (en) * | 2016-09-13 | 2017-02-22 | 重庆理工大学 | Preparation methods and application of rare earth europium complex and fluorescent foam thereof |
| CN108276585A (en) * | 2018-03-10 | 2018-07-13 | 江西师范大学 | A kind of europium coordination polymer and preparation method thereof of detection pH value of water solution |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101368005A (en) * | 2008-09-25 | 2009-02-18 | 湖南大学 | Functional rareearth complexes long-life fluorochrome, synthesis and uses thereof |
| WO2012054648A2 (en) * | 2010-10-19 | 2012-04-26 | Georgia State University Research Foundation, Inc. | Analyte sensors, methods for preparing and using such sensors, and methods of detecting analyte activity |
-
2014
- 2014-11-26 CN CN201410699276.3A patent/CN104359888B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101368005A (en) * | 2008-09-25 | 2009-02-18 | 湖南大学 | Functional rareearth complexes long-life fluorochrome, synthesis and uses thereof |
| WO2012054648A2 (en) * | 2010-10-19 | 2012-04-26 | Georgia State University Research Foundation, Inc. | Analyte sensors, methods for preparing and using such sensors, and methods of detecting analyte activity |
| CN103299193A (en) * | 2010-10-19 | 2013-09-11 | 佐治亚州立大学研究基金会公司 | Analyte sensors, methods for preparing and using such sensors, and methods of detecting analyte activity |
Non-Patent Citations (2)
| Title |
|---|
| 刘静: "新型双功能铕螯合物在时间分辨荧光免疫分析中的应用研究", 《中国优秀硕士学位论文全文数据库 医药卫生科技辑》 * |
| 辛成龙: "新型铕荧光探针的设计合成及其在时间分辨荧光分析中的应用", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106432306A (en) * | 2016-09-13 | 2017-02-22 | 重庆理工大学 | Preparation methods and application of rare earth europium complex and fluorescent foam thereof |
| CN106432306B (en) * | 2016-09-13 | 2019-03-01 | 重庆理工大学 | The preparation method and application of a kind of Rare Earth Europium Complex and its fluorescent foam |
| CN108276585A (en) * | 2018-03-10 | 2018-07-13 | 江西师范大学 | A kind of europium coordination polymer and preparation method thereof of detection pH value of water solution |
| CN108276585B (en) * | 2018-03-10 | 2021-02-26 | 江西师范大学 | Europium coordination polymer for detecting pH value of aqueous solution and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104359888B (en) | 2019-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105255481B (en) | A kind of phenanthro- imidazoles coumarin pair fluorophor ratio fluorescent molecular probe and its synthesis and using method for iron ion detection | |
| Tian et al. | An unusual OFF–ON fluorescence sensor for detecting mercury ions in aqueous media and living cells | |
| US11505530B2 (en) | 1,8-naphthalimide derivative, preparation method therefor and use thereof | |
| CN106008343B (en) | Mercury ion fluorescence probe and its preparation method and application based on naphthalimide | |
| Wang et al. | A dual-responsive and highly sensitive fluorescent probe for Cu2+ and pH based on a dansyl derivative | |
| CN108752377B (en) | Fluorescent probe for detecting peroxynitrite anion, synthetic method and application | |
| CN103772280B (en) | Molecular probe for detecting cyanide ions and synthesis and application method thereof | |
| Sun et al. | A colorimetric and fluorometric dual-modal supramolecular chemosensor and its application for HSA detection | |
| CN109593078B (en) | N-butyl-4-hydroxy-1, 8-naphthalimide-3-formaldehyde- (2-pyridine) hydrazone and application thereof | |
| Wang et al. | Design of a dual-signaling sensing system for fluorescent ratiometric detection of Al 3+ ion based on the inner-filter effect | |
| CN105924449A (en) | Preparation and application for reaction type fluorescein fluorescent probe capable of detecting mercury ions | |
| CN103709321A (en) | Rhodamine B based hydrophilic polymer probe for hyperchromic detection of Cu<2+> as well as preparation method and application thereof | |
| CN110483461A (en) | A kind of detection nitrite ion fluorescence probe and preparation method thereof and application method | |
| Yu et al. | Al (III)-responsive “off–on” chemosensor based on rhodamine derivative and its application in cell imaging | |
| CN105842235A (en) | High-sensitivity fluorescent test paper capable of realizing naked-eye detection of volatile organic amine and preparation thereof | |
| Yu et al. | A novel fluorescent pH probe with valuable p K a based on a twisted intramolecular charge transfer mechanism, and its applications in cell imaging | |
| Arabahmadi et al. | A new fluoride ion colorimetric sensor based on azo–azomethine receptors | |
| CN110698407B (en) | Naked eye or fluorescent Al 3+ Probe and preparation method and application thereof | |
| CN102680466A (en) | Color reaction-based novel NO measuring method | |
| CN104359888A (en) | Lanthanide metal europium ion complex probe-based method for detecting pH value | |
| Kong et al. | A novel phenolphthalein-based fluorescent chemosensor for pyrophosphate detection via an Al3+ displacement approach in real samples and living cells | |
| Han et al. | An AIE-active probe for selective fluorometric–colorimetric detection of HSO3− in aqueous solution and real samples | |
| CN106124466A (en) | The application in detection aniline of the p-phthalic acid europium fluorescent probe containing 1 ethyl 3 Methylimidazole. | |
| CN103232466A (en) | Preparation method of compound (I) 4-hydroxy substituted phenyl imine type rhodamine 6G fluorescence molecule probe and purpose thereof | |
| Hosseini et al. | Selective recognition of mercury in waste water based on fluorescence enhancement chemosensor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 510530 No. 18, Rui Lu, Luogang District, Guangdong, Guangzhou Patentee after: South China Institute of Environmental Science, Ministry of Ecology and Environment Address before: Tianhe District West Village Guangzhou city Guangdong province 510655 No. seven compound Patentee before: South China Institute of Environmental Sciences. MEP |
|
| CP03 | Change of name, title or address | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190405 Termination date: 20201126 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |