CN104359888B - A kind of pH value detection method based on lanthanide series metal europium ion Complex probe - Google Patents
A kind of pH value detection method based on lanthanide series metal europium ion Complex probe Download PDFInfo
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Abstract
The invention discloses a kind of pH value detection methods based on lanthanide series metal europium ion Complex probe.The detection method mainly comprises the steps that the scanning that fluorescence intensity is first carried out to the sample to be tested A comprising lanthanide series metal europium ion complex and different pH value, observe the variation of fluorescence intensity, it realizes to the quantitative detection of solution ph, obtains the linearly interval between pH value and fluorescence intensity；Then the fluorescence intensity of the sample to be tested B comprising lanthanide series metal europium ion complex and water body sample to be measured is detected again, to obtain the pH value of water body sample to be measured.The method of the present invention not only can achieve the detection effect of conventional method, but also have good selectivity；Fast response time, detection time are short, easy to operate and cheap, time-resolved fluorescence signal is strong and stablizes, ensure that experimental method repeatability and fluorescence signal in complex environment can identification so that the practical application of detection method has obtained strong guarantee.
Description
Technical field
The invention belongs to chemical analysis technology fields, and in particular to a kind of based on lanthanide series metal europium ion Complex probe
PH value detection method.
Background technique
PH value, i.e. pH value are the important indicators of water quality.The pH value of natural water is mostly between 6~9；Drinking water pH requirement
Between 6.5~8.5；The pH value of certain industrial waters should ensure that between 7.0~8.5, otherwise will be to metal equipment and pipeline
There is corrosiveness.PH value and acidity, basicity not only had any different but also were related.What pH value indicated is the power of the acid-base property of water, and sour
Degree and basicity are the contents of contained acid or alkaloid substance in water.Degree of the variation of pH value in water quality predictive of water pollution.It is supporting
It grows in water body, pH value very intuitively reflects the variation of water quality, such as the vigor and the existence of carbon dioxide etc. of algae,
It can be inferred whether in the normal range by the size and daily variation of pH value.
The meaning of measurement pH value is that it indicates the essential attribute of dampening；When being abnormal variation, pollution is indicated；Acid
Property water energy promote dissolving metal, be corrosive to metal, thus be possible to cause metal acute and chronic poisoning；Alkaline water energy promotes gold
The precipitation of category, influences the sensory properties of water, and has corrosiveness, and on water correction, pH value influences coagulation and chlorination effect.
China and most countries Drinking Water water standard provide that the range of pH value is 6.5~8.5.It is generally acknowledged that the pH of drinking water
Value will not influence human health and life is drunk in a big way (6.5~9.5).
Other than traditional colorimetric method and pH meter method, in the research that is detected at present to pH value, it is based on fluorescence analysis
Research it is in the majority.There are mainly three types of different types in the method based on fluorescence analysis, the first kind is to measure two kinds not
With the ratio for the fluorescence intensity that dyestuff responds pH value, i.e., usually said Ratio-type pH sensor, the second class is measurement dyestuff
Fluorescence lifetime, third class be directly measurement dyestuff fluorescence intensity.First kind method, i.e. Ratio-type pH sensor, can be very
The problems such as dye leakage and high background signal for being frequently run onto good solution sensor, but how to find two kinds has pH value
The dyestuff of difference response effect, and be applicable in pH sensor, it is a very big problem.Second class method is led to
The fluorescence lifetime of measurement dyestuff is crossed to study pH value, it is strong that the advantage of such method is that fluorescence lifetime does not depend on fluorescence
Degree and wavelength etc. have relative independentability, therefore its interference is smaller.But this method needs high-grade, precision and advanced and complicated instrument to set
It is standby, therefore limit its application in pH detection.So in fact, third class method, i.e., the fluorescence for directly measuring dyestuff are strong
Degree, is to answer method with the most use at present.But this method it is usually used be there is short-life dyestuff, thus detecting
The interference by detection architecture fluorescence itself and organism endogenous fluorescence is easy in, so that the background signal of detection method
It is higher, influence the signal-to-noise ratio of detection method.Therefore, presently, develop a kind of quick, easy, stability and specificity ring
The detection method of pH value is necessary in the water body of border.
Summary of the invention
In order to effectively reduce in environment water detection signal present in pH value detection vulnerable to interference, unstable
And background signal it is strong the problems such as, and improve detection signal can identification and stability, the purpose of the present invention is to provide one
PH value detection method of the kind based on lanthanide series metal europium ion Complex probe.By the method for the invention, realize buffer and
Simple, quick, the stable and specific detection of actual environment water body sample pH value.
For achieving the above object, the present invention adopts the following technical scheme:
A kind of pH value detection method based on lanthanide series metal europium ion Complex probe, successively the following steps are included:
(1) lanthanide series metal europium ion complex is synthesized；
(2) stock solution of lanthanide series metal europium ion complex is prepared；
(3) solution of different pH value is prepared；
(4) the sample to be tested A comprising lanthanide series metal europium ion complex and different pH value is prepared；
(5) variation of fluorescence intensity is observed in the scanning for carrying out fluorescence intensity with Fluorescence Spectrometer to sample to be tested A, is realized
To the quantitative detection of solution ph, the linearly interval between pH value and fluorescence intensity is obtained；
(6) prepare water body sample to be measured；
(7) the sample to be tested B comprising lanthanide series metal europium ion complex and water body sample to be measured is prepared；
(8) obtained fluorescence intensity is compared step by the scanning for carrying out fluorescence intensity with Fluorescence Spectrometer to sample to be tested B
(5) linearly interval obtained obtains the pH value of water body sample to be measured.
Preferably, specific step is as follows for the step (1): by 88mg Eu2O3It dissolves by heating in 2.0mL concentrated hydrochloric acid,
After heating removes extra concentrated hydrochloric acid, ethyl alcohol is added to dilute to obtain clear solution, i.e. EuCl3Ethanol solution；Separately use 20mL ethyl alcohol
It dissolves 337mg TTA (thioyl trifluoroacetone), by EuCl3Ethanol solution and the ethanol solution of TTA be added to there-necked flask
In, heating water bath, magnetic agitation, controlled at 60 DEG C, adjusting pH value with NaOH solution is 6.0, controls temperature and pH value, instead
After answering 40min, 5-NH is separately dissolved with 15mL ethyl alcohol2Then-phen is added dropwise in reaction system, control reaction temperature at this time and be
58 DEG C, the reaction was continued, and 5h is stood overnight in refrigerator after completion of the reaction, there is yellow solid precipitation, is filtered；With ethyl alcohol and ultrapure water
Washing, is dried in vacuo at 50 DEG C, then with ethyl alcohol recrystallization 2 times, obtains having the yellow solid of long-life phosphors performance i.e.
For the lanthanide series metal europium ion complex Eu (TTA)3(5-NH2- phen), it is indicated with ETN.
It is furthermore preferred that the 5-NH2- phen is made by following methods: being passed through with phen (1,10- phenanthroline) for raw material
5-NO is made in nitration reaction2Then the 5-NH is made by reduction reaction in-phen2-phen。
More preferably, the nitration reaction is using the concentrated sulfuric acid and concentrated nitric acid mixed acid as nitrating agent, and the reaction time is
45min, reaction temperature are 165 DEG C；The reduction reaction be 5% using mass fraction containing palladium palladium carbon as catalyst, hydration
Hydrazine is reducing agent, and reaction time 5.0h, reaction temperature is 90~92 DEG C.
Preferably, the stock solution of lanthanide series metal europium ion complex described in step (2) is prepared: accurately weighing 5.065mg
ETN solid powder made from step (1), is dissolved into 100mL volumetric flask with ethyl alcohol, and obtaining concentration is 5 × 10-5mol·L-1's
The stock solution of lanthanide series metal europium ion complex.
Preferably, the preparation of different pH value described in step (3): pH value is at 1.98~11.98 by B-R buffer
It is formulated, other pH value are adjusted by HCl and NaOH solution；
B-R the buffer is 0.04molL by concentration-1Phosphoric acid, boric acid and acetic acid mixed acid, use 0.2mol
L-1NaOH adjusting is formed to required pH value；Other pH value solution are by 2.0molL-1HCl and 2.0molL-1NaOH is adjusted
It forms.
It is furthermore preferred that the pH value of the 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 preparation of sample to be tested A described in step (4) are as follows: prepare in a series of 10mL colorimetric cylinders, point
Not Jia Ru lanthanide series metal europium ion complex made from 1.0mL step (2) stock solution, be put into 60 DEG C of baking ovens that remove ethyl alcohol molten
Agent, then respectively with the solution constant volume of the different pH value of step (3) preparation to scale.
Preferably, step (5) detection to solution ph specifically: be made with Fluorescence Spectrometer determination step (4)
Testing sample solution time-resolved fluorescence intensity variation and record, maximum excitation wavelength and maximum emission wavelength point
Not Wei 355nm and 611nm, delay time 0.1ms, exciting slit and transmite slit are 5.0nm, to realize to sample to be tested
The quantitative detection of solution ph obtains the linearly interval between pH value and fluorescence intensity.
It is furthermore preferred that the linearly interval of the pH value and fluorescence intensity is respectively as follows: pH 1.5~7.5,10~14.
Preferably, step (6) the water body sample to be measured are as follows: sewage, river water, spring, lake water or originally water sample.Wherein
Spring and originally water sample does not pre-process, sewage, river water and lake water sample first filter, then in supercentrifuge
Centrifugation removes visible suspended matter on (12000rpm/min, 5min).
Preferably, the preparation steps of sample to be tested B described in step (7) are similar with step (4), only will be in step (4)
Different pH value is changed to water body water sample to be measured, specifically: prepare a series of 10mL colorimetric cylinders, is separately added into 1.0mL step (2)
The stock solution of lanthanide series metal europium ion complex obtained is put into 60 DEG C of baking ovens and removes alcohol solvent, then uses step respectively
(6) the water body sample constant volume to be measured prepared is to scale；The scanning step of step (8) fluorescence intensity to sample to be tested B with
Step (5) is similar, the condition of scanning is identical, before difference is actual scanning, first makees pre-detection with wide pH value test paper with rough estimate
The pH size of sample.
The principle of the present invention are as follows: since the background fluorescence of detection architecture itself and the intracorporal endogenous fluorescence of biology etc. are all
Short-life fluorescence signal, if it is possible to glimmering using time resolution using the substance with long-life phosphors characteristic as dyestuff
Optical mode removes or reduces the interference of short-life background fluorescence signal, then to the specificity and reality of detection method
Application will have huge raising.Discovery lanthanide series metal europium ion complex not only has fluorescence lifetime length, fluorescence under study for action
The advantages that quantum yield height and fluorescence signal are stablized, and when pH value changes, time-resolved fluorescence intensity has fast
Fast sensitive response.Therefore, the present invention is proposed a kind of easy, fast using long-term durability luminous lanthanide series metal europium ion complex
The detection method of pH value in speed, stable and specificity environment water.
Compared with prior art, the present invention has the following advantages and beneficial effects:
(1) detection method is simple, responds to pH value rapid；
(2) high specificity, other organic matters and inorganic matter etc. present in solution do not influence testing result；
(3) cheap, only lanthanide series metal europium ion complex need to be synthesized with simply and easily method；
(4) it is convenient to operate, without complicated Sample pretreatment；
(5) it can be applied to the pH value detection in actual environment water body；
(6) time-resolved fluorescence signal is strong and stablizes, and the repeatability and fluorescence signal that ensure that experimental method are in complexity
In environment can identification so that the practical application of detection method has obtained strong guarantee.
The method of the present invention is compared with the traditional method, and not only can achieve the detection effect of conventional method, but also is had good
Selectivity；Meanwhile the method for the present invention fast response time, detection time are short, easy to operate and cheap, it is often more important that this
Inventive method utilizes the long-term durability luminous property that has of lanthanide series metal europium ion complex, with time-resolved fluoroimmunoassay,
It is effectively reduced or is eliminated the interference of background fluorescence signal, improves the intensity and stability of detection signal, so that inspection
The use of survey method in practical applications has obtained effectively guaranteeing.
Detailed description of the invention
Fig. 1 is lanthanide series metal europium ion complex Eu (TTA) used in the present invention3(5-NH2- phen) structural formula.
Fig. 2 is lanthanide series metal europium ion complex Eu (TTA) used in the present invention3(5-NH2- phen) synthesis step.
Fig. 3 be in the present invention dissolved oxygen and ionic strength to the interference figure of detection method.
Fig. 4 is the time-resolved fluorescence launching light spectrogram of different pH value detections in the present invention.
Fig. 5 is the curve graph and range of linearity figure of detection method in the present invention.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
It is instrument and equipment used in the embodiment of the present invention of part below, other experiment conditions being not specified are according to routine
Or with condition proposed by its manufacturer: Perkin-Elmer LS-55 phosphorescence spectrophotometer (Britain)；
Centrifuge 5417R small desk high speed freezing centrifuge (German Eppendorf company)；Merck Millipore is ultrapure
Water dispenser (Germany)；PHS-3B type pH meter (Shanghai Precision Scientific Apparatus Co., Ltd)；Electronic balance TE124S (Germany
Sartorius company).
Embodiment 1
With thioyl trifluoroacetone (TTA), 1,10- phenanthroline (phen) is that the lanthanide series metal europium ion of ligand cooperates
Object: Eu (TTA)3(5-NH2- phen) preparation, the specific steps are as follows:
It a. is the 5-NH of raw material with 1,10- phenanthroline (phen)2The synthesis of-phen
Synthesis step: (1) nitration of phen.The 13mL concentrated sulfuric acid is added into 250mL three-necked flask, in magnetic agitation item
Under part, 2.0g phen is added portionwise, magnetic agitation dissolution slowly heats up, when temperature is raised to 150 DEG C, is slowly added to 5.5mL
Concentrated nitric acid, reaction temperature are controlled at 165 DEG C, the reaction was continued 45min.After completion of the reaction, reaction solution is carefully poured into 130g ice water
In mixture, after trash ice melts completely, 2.0molL is used-1It is 7.0 that NaOH solution, which adjusts pH value, has a large amount of yellow heavy at this time
It forms sediment and generates, decompression filters, washing, air-dries in air and obtains crude product NO2- phen obtains yellow crystals with ethyl alcohol recrystallization 2 times,
60 DEG C of vacuum dryings, as NO2-phen。(2)NO2- phen is reduced to NH2-phen.30mL is added into 250mL three-necked flask
Then 1.6g NO is added in ethyl alcohol2- phen is dissolved by heating under stirring condition, 0.5g Pd/C is then added, and be warming up to reflux
State continues to stir 10min, then 10mL is added dropwise with hydrazine hydrate/ethanol solution that 1:1 is matched in 60min, keeps
Reflux state 5.0h.Decompression filters while hot after completion of the reaction, obtains orange-red solution；By the distillation of this solution to there is a large amount of yellow to sink
It forms sediment and generates, then stood overnight in refrigerator, filtered, dry, ethyl alcohol recrystallization 2 times, vacuum drying obtains crystal at 60 DEG C.
B. lanthanide series metal europium ion complex Eu (TTA)3(5-NH2- phen) synthesis
Synthesis step: 88mg Eu is weighed2O3It dissolves by heating in 2.0mL concentrated hydrochloric acid, after heating removes extra concentrated hydrochloric acid,
Ethyl alcohol is added to dilute to obtain clear solution, i.e. EuCl3Ethanol solution.337mg TTA is separately dissolved with 20mL ethyl alcohol.By EuCl3Ethyl alcohol
The ethanol solution of solution and TTA are added in there-necked flask slowly, heating water bath, magnetic agitation, controlled at 60 DEG C, are used
2.0mol·L-1It is 6.0 that NaOH solution, which adjusts pH value, controls temperature and pH value, reacts 40min.After 40min, separately with 15mL ethyl alcohol
Dissolve 5-NH2Then-phen is added dropwise in reaction system, controlling reaction temperature at this time is 58 DEG C of the reaction was continued 5h, end of reaction
Afterwards, it is stood overnight in refrigerator, there is the solid of yellow to be precipitated, filter.With ethyl alcohol and milli-Q water, it is dried in vacuo at 50 DEG C,
Then with ethyl alcohol recrystallization 2 times, the yellow solid with long-life phosphors performance is obtained --- Eu (TTA)3(5-NH2- phen),
It is indicated with ETN, structural formula is as shown in Fig. 1.Above-mentioned synthesis step is as shown in Fig. 2.
The stability study of embodiment 2:ETN time-resolved fluorescence intensity
10 different 10mL colorimetric cylinders are taken, the stock solution of 1.0mL ETN is separately added into, is put into 60 DEG C of baking ovens and removes second
Alcoholic solvent.B-R buffer the constant volume for being then 7.5 with pH value sufficiently dissolves and is uniformly mixed, stand 10min at room temperature to scale,
After ETN sufficiently dissolves and stablizes, 3.0mL solution is successively taken to be added in 1-cm cuvette, with Perkin-Elmer LS-55
The variation of its time-resolved fluorescence intensity of phosphorescence spectrophotometric determination is simultaneously recorded, maximum excitation wavelength and maximum hair
Long ejected wave is respectively 355nm and 611nm, slit 5.0nm, delay time 0.1ms.To obtain 10 different times point
It distinguishes fluorescence intensity level, relative standard deviation calculating is carried out to it, relative standard deviation 3.2%, less than 5%, as a result explanation should
Method is with good stability.
Embodiment 3: dissolved oxygen and ionic strength affect research
A. influence research of the dissolved oxygen to 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 the saturation of the air is molten
Liquid.The pH value of 3 kinds of solution is controlled 7.0.Then the time according to the step method measurement ETN of embodiment 2 in this 3 kinds of solution
Resolved fluorometric intensity, to influence to study on it.As a result it is recorded in the A figure of attached drawing 3.As the result is shown in 3 kinds of solution
The time-resolved fluorescence intensity of ETN is basically unchanged, to absolutely prove that oxygen concentration in solution can be with to the interference of detection method
It ignores, dissolved oxygen can not be considered to influence of the invention in actually detected.
B. influence research of the ionic strength to ETN time-resolved fluorescence intensity
The present embodiment prepared 19 kinds of various concentrations NaCl solution (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 influence to the time-resolved fluorescence intensity of ETN.The pH value of this 19 kinds of solution is controlled 6.5.Then according to the step of embodiment 2
Time-resolved fluorescence intensity of the rapid method measurement ETN in this 19 kinds of solution, to influence to study on it.As a result it is recorded in
In the B figure of attached drawing 3.The time-resolved fluorescence intensity of the ETN in 19 kinds of solution is basically unchanged as the result is shown, to absolutely prove molten
It is lower than 1.0molL in liquid-1Ionic strength the interference of detection method can be ignored, can not examine in actually detected
Ionic strength is considered to influence of the invention.
Embodiment 4: the detection research of different pH value
In order to analyze the response for verifying method proposed by the present invention to different pH value, the present embodiment prepared pH value from
1.98 to 11.98 B-R buffer and with HCl and NaOH adjust pH other pH value (pH value is respectively 0,0.5,1.0,
1.5,12.5,13.0,13.5 with solution 14.0).Then, the stock solution for taking 1.0mL ETN respectively, be added to 28 it is different
In 10mL colorimetric cylinder, it is put into 60 DEG C of baking ovens and removes alcohol solvent.Then respectively with the solution constant volume of different pH value to scale, fill
Divide dissolution to be uniformly mixed, stands 10min at room temperature, after ETN sufficiently dissolves and stablizes, successively taken respectively from low to high according to pH value
3.0mL solution is added in 1-cm cuvette, with Perkin-Elmer LS-55 phosphorescence its time of spectrophotometric determination
Resolved fluorometric intensity is simultaneously recorded, and maximum excitation wavelength and maximum emission wavelength are respectively 355nm and 611nm, exciting slit
As a result remember for 5.0nm, delay time 0.1ms to obtain 28 different time-resolved fluorescence intensity values with transmite slit
Record is in figure 4.PH value and time-resolved fluorescence intensity have apparent corresponding relationship, time it can be seen from the A figure of attached drawing 4
Resolved fluorometric intensity value is increased with the raising of pH, and when pH is between 7.5 to 9.5, time-resolved fluorescence intensity reaches most
Big value.It can be seen from the B figure of attached drawing 4 after pH value is more than 9.5, with the lasting raising of pH value, time-resolved fluorescence is strong
Degree significantly reduces.It can be seen from the figure that this method is rapid for the response of pH value, and signal stabilization, signal-to-noise ratio height.
Embodiment 5: the linear analysis of detection method
The relationship of pH value and time-resolved fluorescence intensity is as shown in the A figure of attached drawing 5.It can be seen that from the A figure of attached drawing 5
The curve is divided into four parts, and first part is pH 0~1.5, and time-resolved fluorescence intensity shows herein nearly close to 0 at this time
Under the conditions of, the time-resolved fluorescence intensity of ETN is almost quenched completely；Second part is pH 1.5~7.5, this stage is with pH
The time-resolved fluorescence intensity of the raising of value, ETN also significantly increases, and within this range, time-resolved fluorescence intensity and pH
Good linear relationship is presented in value, and linear equation and related coefficient are as shown in the B figure of attached drawing 5；Part III be pH 7.5~
9.5, the time-resolved fluorescence intensity of ETN reaches maximum value at this time；Part IV is pH 9.5~14, when pH is greater than 9.5,
The time-resolved fluorescence intensity of ETN is reduced with the raising of pH value, and when pH value is between 10 to 14, time-resolved fluorescence is strong
Good linear relationship is presented with pH value in degree, and linear equation and related coefficient are as shown in the B figure of attached drawing 5.
Embodiment 6: Evaluation on specificity
In order to explore specificity of the invention, the present embodiment has selected a series of organic matters and inorganic matter chaff interferent to this hair
Method in bright carries out special Journal of Sex Research.In this experiment, pH is controlled 7.0.As a result it is recorded in table 1.It can from table 1
Out, a series of influence of the presence of listed organic matters and inorganic matter to the detection research of pH value can be ignored substantially, opposite to mark
Quasi- absolute value of the difference partially is between 0.07%~2.77%, less than 5%.So detection method proposed by the present invention has well
Anti-interference ability, ensure that its application study in actual environment water sample.
1 Evaluation on specificity experimental result of table
Embodiment 7: the detection research of actual environment water body sample pH value
In order to verify the practical application of method proposed by the present invention, 5 kinds of different actual environments are employed herein
Water sample sample, respectively sewage, river water, spring, lake water and originally water sample.Wherein spring and originally water sample does not do pre- place
Reason, sewage, river water and lake water sample first filter, and then centrifugation removal can on supercentrifuge (12000rpm/min, 5min)
The suspended matter seen.Before actually detected, first make pre-detection with wide pH value test paper, testing result shows that the pH of sewage is greater than 9, other
Water sample pH is respectively less than 8.Then pH value detection has been carried out to this 5 kinds of environment water samples with the step method in embodiment 2 and 4,
And the result measured by the testing result of method of the invention and pH meter comparative study is subjected to.As a result it is recorded in table 2.
From table 2 it can be seen that result measured by the testing result and pH meter of method proposed by the present invention has good consistency.Knot
Fruit absolutely proves that detection method proposed by the present invention has good practical application.
The comparison of 2 actual environment water body testing result of table
| Sample | pHa | pHb | Deviation |
| Sewage | 10.87 | 10.79 | 0.08 |
| River water | 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, pHaIndicate the result measured using the present invention；pHbIndicate the result that pH meter measures
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (3)
1. a kind of pH value detection method based on lanthanide series metal europium ion Complex probe, which is characterized in that successively include following
Step:
(1) lanthanide series metal europium ion complex Eu (TTA) is synthesized3(5-NH2- phen), Eu (TTA)3(5-NH2- phen) structure
Formula is
(2) compound concentration is 5 × 10-5mol·L-1Lanthanide series metal europium ion complex stock solution；
(3) solution of different pH value is prepared；PH value is formed at 1.98~11.98 by B-R buffer, other pH value by
HCl and NaOH solution are adjusted；The pH value of the 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；
(4) the sample to be tested A comprising lanthanide series metal europium ion complex and different pH value is prepared；The preparation of sample to be tested A
The step of are as follows: prepare a series of 10mL colorimetric cylinders, is separately added into lanthanide series metal europium ion complex made from 1.0mL step (2)
Stock solution, be put into 60 DEG C of baking ovens and remove alcohol solvent, then respectively with step (3) prepare different pH value solution constant volume
To scale；
(5) variation of fluorescence intensity is observed in the scanning for carrying out fluorescence intensity with Fluorescence Spectrometer to sample to be tested A, is realized to molten
The quantitative detection of liquid pH value obtains the linearly interval between pH value and fluorescence intensity；The fluorescence intensity condition of scanning are as follows: maximum
Excitation wavelength and maximum emission wavelength are respectively 355nm and 611nm, and delay time 0.1ms, exciting slit and transmite slit are
5.0nm；The linearly interval of the pH value and fluorescence intensity is respectively as follows: pH 1.5~7.5,10~14；
(6) prepare water body sample to be measured；The water body sample to be measured is sewage, river water, spring, lake water or originally water sample；
(7) the sample to be tested B comprising lanthanide series metal europium ion complex and water body sample to be measured is prepared；The preparation of sample to be tested B
A series of step are as follows: prepare 10mL colorimetric cylinders, be separately added into lanthanide series metal europium ion complex made from 1.0mL step (2)
Stock solution is put into 60 DEG C of baking ovens and removes alcohol solvent, then respectively with the water body sample constant volume to be measured of step (6) preparation to quarter
Degree；
(8) scanning of fluorescence intensity is carried out with Fluorescence Spectrometer to sample to be tested B, step (8) is described to sample to be tested B's
The scanning step of fluorescence intensity are as follows: first make pre-detection with rough estimate pH size, then according to step with wide pH value test paper
(5) the fluorescence intensity condition of scanning is scanned；The linearly interval that obtained fluorescence intensity comparison step (5) is obtained,
Obtain the pH value of water body sample to be measured.
2. the pH value detection method according to claim 1 based on lanthanide series metal europium ion Complex probe, feature exist
In the stock solution preparation steps of lanthanide series metal europium ion complex described in step (2) are as follows: weigh 5.065mg step (1) and be made
Lanthanide series metal europium ion complex, be dissolved into 100mL volumetric flask with ethyl alcohol, obtain concentration be 5 × 10-5mol·L-1Lanthanum
It is the stock solution of Europium Metal ionic complex.
3. the pH value detection method according to claim 1 based on lanthanide series metal europium ion Complex probe, feature exist
In step (3) B-R buffer is 0.04molL by concentration-1Phosphoric acid, boric acid and acetic acid mixed acid, use
0.2mol·L-1NaOH adjusting is formed to required pH value；Other pH value solution are by 2.0molL-1HCl and 2.0molL- 1NaOH is adjusted.
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| 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 |
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| 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 |
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| 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;刘静;《中国优秀硕士学位论文全文数据库 医药卫生科技辑》;20130515(第5期);E060-12 |
| 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;辛成龙;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20110915(第9期);B014-39 |
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