CN104807789B - The detection method of high sensitivity heavy metal in water content - Google Patents
The detection method of high sensitivity heavy metal in water content Download PDFInfo
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Abstract
The present invention discloses a kind of detection method of high sensitivity heavy metal in water content, including：50nM papains and the first activation mixed liquor are stirred to form Eu3+The papain of salt modification, Eu3+The papain of salt modification obtains Eu after purification through bag filter filtering3+The papain of salt modification；50nM papains are stirred with the described second activation mixed liquor reacts the papain for forming fluorescent dye XL665 modifications under conditions of 20 DEG C ~ 30 DEG C, and the molar ratio of fluorescent dye XL665 and papain is 1：5；By Eu3+The papain of salt modification and the papain of fluorescent dye XL665 modifications are mixed to form fluoroscopic examination liquid, Eu3+The papain that the papain of salt modification is modified with fluorescent dye XL665 is according to 1：1 mol ratio is sufficiently mixed.The inventive method has fast speed, high sensitivity, the range of linearity is wide, use cost is low, can realize Site Detection, improves heavy metal ions in wastewater detection efficiency, promptness and detection sensitivity.
Description
Technical field
The present invention relates to water body to detect environmental area, and in particular to a kind of detection side of high sensitivity heavy metal in water content
Method.
Background technology
At present due to the weight in the industry such as exploitation of mineral resources, smelting processing, machine-building and instrument and meter, organic synthesis
Metallic wastewater discharges, and causes much by heavy metal（Such as lead, mercury, cadmium, cobalt）Caused water environment pollution.Heavy metal wastewater thereby is pair
Environmental pollution most serious and the mankind are endangered with one of maximum industrial wastewater, thus the concentration of lead, mercury, cadmium, cobalt plasma also into
For the important indicator of monitoring water environment.By detecting the concentration of lead in water body, mercury, cadmium, cobalt plasma, so as to substantially reflect
The heavy metal pollution degree of water body.The standard method of analysis of traditional heavy metal monitoring is mainly with AAS and Atomic absorption
Based on AAS, the material is carried out using specific absorption of the measured matter in certain wave strong point or a wavelength range
Qualitative and quantitative analysis.The continuous progress of science and technology at any time, the more other method of domestic application also have atomic absorption method, original
Sub- fluorescence method and more advanced inductively coupled plasma emission spectrography (ICP-AES), inductively coupled plasma mass spectrometry
The analysis methods such as method (ICP-MS).Expensive for such large scale equipment, complex operation, maintenance are big, cost is higher, are not easy to realize
The drawbacks such as Site Detection.
The content of the invention
The present invention provides a kind of detection method of high sensitivity heavy metal in water content, this detection method have speed it is fast,
High sensitivity, the range of linearity are wide, use cost is low, can realize Site Detection, improve heavy metal ions in wastewater detection effect
Rate, promptness and detection sensitivity.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：A kind of inspection of high sensitivity heavy metal in water content
Survey method, comprises the following steps：
Step 1. will contain Eu3+The europium cryptate of ion and 300nM 1-（3- dimethylamino-propyls）- 3- ethyls
It is mixed that Carbodiimide solution and 300nM N- hydroxy thiosuccinimide solution are stirred activation 30min the first activation of formation
Close liquid；
50nM papains are stirred the condition at 20 DEG C ~ 30 DEG C by step 2. with the described first activation mixed liquor
Lower coupling reaction forms Eu3+The papain of salt modification, it is described to contain Eu3+The europium cryptate and Papain of ion
The molar ratio of enzyme is 1：5, it is described to contain Eu3+The europium cryptate and 1- of ion（3- dimethylamino-propyls）- 3- ethyl carbon
The molar ratio of diimine and N- hydroxy thiosuccinimides is 1：2 ~ 5, the Eu3+The papain of salt modification is through dialysis
Bag filtering obtains Eu after purification3+The papain of salt modification；
Step 3. is by fluorescent dye XL665 and 300nM 1-（3- dimethylamino-propyls）- 3- ethyl carbodiimide solution
Activation 30min, which is stirred, with 300nM N- hydroxy thiosuccinimide solution forms the second activation mixed liquor；
50nM papains are stirred the condition at 20 DEG C ~ 30 DEG C by step 4. with the described second activation mixed liquor
Lower coupling reaction forms the papain of fluorescent dye XL665 modifications, the fluorescent dye XL665 and pawpaw egg in step 4
The molar ratio of white enzyme is 1：5, the fluorescent dye XL665 and 1-（3- dimethylamino-propyls）- 3- ethyl carbodiimides and N-
The molar ratio of hydroxy thiosuccinimide is 1：2~5；
Step 5. is by the Eu3+The papain of salt modification and the papain that fluorescent dye XL665 is modified are abundant
It is mixed to form fluoroscopic examination liquid, the Eu3+The papain of salt modification is pressed with the fluorescent dye XL665 papains modified
According to 1：1 mol ratio is sufficiently mixed；
The fluoroscopic examination liquid is added after the aqueous solution to be detected the excitation source passed through and excited so as to detect by step 6.
The fluorescent emission intensity of 620nm and 665nm wavelength, and calculate 665nm fluorescent emission intensities and 620nm fluorescent emission intensity ratios
Obtain prepare liquid fluorescence ratio；
Step 7. is by prepare liquid fluorescence ratio and standard fluorescence curve comparison so as to obtaining heavy metal in the aqueous solution to be detected
The concentration of ion, the standard fluorescence curve are the standard liquid based on several known heavy metal concentration and the fluoroscopic examination
The fluorescence curve that the liquid fluorescence ratio that liquid obtains calibrates.
Further improvement project in above-mentioned technical proposal is as follows：
1. in such scheme, the papain of the modifications of XL665 described in step 4 obtains after purification through bag filter filtering
XL665 modification papain.
2. in such scheme, the heavy metal includes Hg2+、Cu2+、Pb2+。
3. in such scheme, the stir speed (S.S.) of step 1 ~ 4 is 300rpm.
4. in such scheme, optical source wavelength caused by excitation source is 360nm in the step 6.
5. in such scheme, the time of coupling reaction is 2 h in the step 2, step 4.
6. in such scheme, the temperature of coupling reaction is 25 DEG C in the step 2, step 4.
Because above-mentioned technical proposal is used, the present invention has following advantages and effect compared with prior art：
1. the detection method of high sensitivity heavy metal in water content of the present invention, its Heavy Metals in Waters ion to be detected makes
Obtain papain, the Eu of fluorescent dye XL665 modifications3+The papain aggregation of salt modification, so as to further between the two
Distance, the characteristic of the fluorescence resonance energy transfer between Eu3+ salt and XL665 is produced when causing two fluorophors close, swashed
Portion of energy during hair by cryptate capture discharges, launch wavelength 620nm；Another part energy transfer to XL665 or
Fluorescent dye d2, launch wavelength 665nm, so as to reach the purpose detected to the heavy metal substance in water body environment, carry
High heavy metal ions in wastewater detection efficiency, promptness and detection sensitivity.
2. the detection method of high sensitivity heavy metal in water content of the present invention, Eu3+The molar ratio of salt and papain is 1:
5, Eu3+Salt and 1-（3- dimethylamino-propyls）- 3- ethyl carbodiimides solution and N- hydroxy thiosuccinimide solution -3- second
The ratio of base Carbodiimide solution is 1:2 ~ 5 this ratios can fully activate Eu3+Salt surface amino groups group, papain excessively may be used
To increase the joint efficiency of Eu3+ salt and papain, reagent both will not be excessively wasted；Again will not adding because of the activator of excess
Enter to influence Eu3+The properties of product of salt and fluorescent dye XL665；Secondly, 1- in the present invention（3- dimethylamino-propyls）- 3- ethyl carbon
Diimine solution and N- hydroxy thiosuccinimides solution and Eu3+The mol ratio of salt is 2 ~ 5:1, fluorescent dye XL665 with
1-（3- dimethylamino-propyls）The mol ratio of -3- ethyl carbodiimides solution and 300nM N- hydroxy thiosuccinimides is equal
For 1:2 ~ 5, Eu can be activated3+Salt surface amino groups group, so as to which the carboxylic group with papain surface is coupled；Secondly；Institute
State in scheme, stir speed (S.S.) 300rpm, each material can be made fully to react, improve coupling efficiency, light caused by excitation source
Source wavelength is 360nm, 360nm Eu3+Again, the time for selecting excellent coupling reaction is 2 h to the excitation wave of ion, makes that each thing can be made
Matter is fully reacted, and will not reduce each species activity due to the reaction time of overlength again.
Brief description of the drawings
Accompanying drawing 1 is reaction principle schematic diagram of the present invention；
Accompanying drawing 2 is that standard curve of the present invention calculates schematic diagram；
Accompanying drawing 3 is obtained fluorescence spectra in the presence of heavy metal free ion；
Accompanying drawing 4 is obtained fluorescence spectra in the presence of heavy metal ion of the present invention.
Embodiment
Below in conjunction with the accompanying drawings and embodiment the invention will be further described：
Embodiment：A kind of detection method of high sensitivity heavy metal in water content, comprises the following steps：
Step 1. will contain Eu3+The europium cryptate of ion and 300nM 1-（3- dimethylamino-propyls）- 3- ethyls
It is mixed that Carbodiimide solution and 300nM N- hydroxy thiosuccinimide solution are stirred activation 30min the first activation of formation
Close liquid；
50nM papains are stirred the condition at 20 DEG C ~ 30 DEG C by step 2. with the described first activation mixed liquor
Lower coupling reaction forms Eu3+The papain of salt modification, it is described to contain Eu3+The europium cryptate and Papain of ion
The molar ratio of enzyme is 1：5, it is described to contain Eu3+The europium cryptate and 1- of ion（3- dimethylamino-propyls）- 3- ethyl carbon
The molar ratio of diimine and N- hydroxy thiosuccinimides is 1：2~5；Eu described in step 23+The Papain of salt modification
Enzyme obtains Eu after purification through bag filter filtering3+The papain of salt modification；
Step 3. is by fluorescent dye XL665 and 300nM 1-（3- dimethylamino-propyls）- 3- ethyl carbodiimide solution
Activation 30min, which is stirred, with 300nM N- hydroxy thiosuccinimide solution forms the second activation mixed liquor；
50nM papains are stirred the condition at 20 DEG C ~ 30 DEG C by step 4. with the described second activation mixed liquor
Lower coupling reaction forms the papain of fluorescent dye XL665 modifications, the fluorescent dye XL665 and pawpaw egg in step 4
The molar ratio of white enzyme is 1：5, the fluorescent dye XL665 and 1-（3- dimethylamino-propyls）- 3- ethyl carbodiimides and N-
The molar ratio of hydroxy thiosuccinimide is 1：2~5；The papain of the modifications of XL665 described in step 4 is through bag filter
Filtering obtains the papain of XL665 modifications after purification；
Step 5. is by the Eu3+The papain of salt modification and the papain that fluorescent dye XL665 is modified are abundant
It is mixed to form fluoroscopic examination liquid, the Eu3+The papain of salt modification is pressed with the fluorescent dye XL665 papains modified
According to 1：1 mol ratio is sufficiently mixed；
The fluoroscopic examination liquid is added after the aqueous solution to be detected the excitation source passed through and excited so as to detect by step 6.
The fluorescent emission intensity of 620nm and 665nm wavelength, and calculate 665nm fluorescent emission intensities and 620nm fluorescent emission intensity ratios
Obtain prepare liquid fluorescence ratio；
Step 7. is by prepare liquid fluorescence ratio and standard fluorescence curve comparison so as to obtaining heavy metal in the aqueous solution to be detected
The concentration of ion, the standard fluorescence curve are the standard liquid based on several known heavy metal concentration and the fluoroscopic examination
The fluorescence curve that the liquid fluorescence ratio that liquid obtains calibrates.
Above-mentioned heavy metal includes Hg2+、Cu2+、Pb2+；The stir speed (S.S.) of above-mentioned steps 1 ~ 4 is 300rpm.
Optical source wavelength caused by excitation source is 360nm in above-mentioned steps 6.Coupling reaction in above-mentioned steps 2, step 4
Time is 2h.
The temperature of coupling reaction is 25 DEG C in above-mentioned steps 2, step 4.
Above content is further described below.
Reaction principle is as shown in figure 1, the papain amounts of components of Eu3+ salt modification, concentration is as shown in table 1.
Table 1
| Reagent | Concentration | Molar ratio |
| Eu3+ salt | 0.68uM | 1（Final concentration of 10nM） |
| Papain | 1 uM | 5 |
| 1-（3- dimethylamino-propyls）- 3- ethyl carbodiimides | 1 uM is dissolved in PBS（pH7.4） | 20~50 |
| N- hydroxy thiosuccinimides | 1 uM is dissolved in PBS（pH7.4）UM, i.e. umol/L | 20~50 |
Papain amounts of components, the concentration of fluorescent dye XL665 modifications are as shown in table 2：
Table 2
| Reagent | Concentration | Molar ratio |
| XL665 | 0.1uM | 1（Final concentration of 10nM） |
| Papain | 1uM | 5 |
| 1-（3- dimethylamino-propyls）- 3- ethyl carbodiimides | 1 uM | 20~50 |
| N- hydroxy thiosuccinimides | 1 uM | 20~50 |
The present embodiment standard curve is drawn as follows：By Eu3+Salt modifying pawpaw enzyme and fluorescent dye XL665 modifications
Papain mixed solution in add various concentrations heavy metal ion, respectively 0.1 nM, 1 nM, 10 nM, 100 nM, 1
NM, excited with 360nm excitation source, Detection wavelength and calculates 665nm/ in 620nm and 665nm fluorescent emission intensity
The ratio of 620nm fluorescence intensities.Standard curve is drawn according to ratio.
（1）By Eu3+Salt（Final concentration of 10nM）It is added in reactor；Add 300nM EDC solution and 300nM
Sulfo-NHS solution, activate 30min；50nM papains are added, continues concussion and is well mixed, 300rpm, 25 DEG C, 2h, each reaction
Thing molar concentration rate is：Eu3+Salt:Papain:EDC:sulfo-NHS=1:5:30:30, it is unnecessary that the purifying of sample bag filter removes
Papain and activator 48h, so as to remove unnecessary papain and activator, obtain the pawpaw enzyme modification Eu3+ salt of purifying.
（2）By fluorescent dye XL665（Final concentration of 10nM）It is added in reactor；Add 300nM EDC solution and
300nM sulfo-NHS solution, activate 30min；50nM papains are added, continues concussion and is well mixed, 300rpm, 25 DEG C, 2h,
Each reactant molar concentration rate is：XL665：Papain：EDC：sulfo-NHS=1:5:30:30, this ratio can fully live
Change XL665 surface amino groups groups, coupling efficiency can be improved, will not excessively waste reagent again, the purifying of sample bag filter removes more
Remaining papain and activator 48h, so as to remove unnecessary papain and activator, obtain the pawpaw enzyme modification XL665 of purifying.
（3）The Eu that above-mentioned steps are obtained3+Salt modifying pawpaw enzyme and XL665 modifying pawpaw enzymes are sufficiently mixed, and detect fluorescence
Detection signal, as shown in Fig. 2 y=0.318x+4.268 is standard curve calculation formula in Fig. 2, step 5 in example 1 is obtained
665nm/620nm ratios are brought into be substituted into this formula as y values, and it is heavy metal substance in testing sample that x values, which are calculated,
Concentration, R2 is the linearly dependent coefficient of this formula, the statistical analysis index of dependency relation level of intimate between x, y；
（4）The heavy metal ion of various concentrations is separately added into above-mentioned mixed solution, such as 0.1 nM, 1 nM, 10 nM,
100 nM, 1 uM, are excited with 360nm excitation source, and Detection wavelength and is calculated in 620nm and 665nm fluorescent emission intensity
The ratio of 665nm/620nm fluorescence intensities.Standard curve is drawn as reference according to ratio, to calculate the middle weight of testing sample
Concentration of metal ions, standard curve act on for contrast, and the ratio for the 665nm/620nm that test sample is obtained is brought into standard song
In line equation, by the concentration that can be calculated heavy metal in waste water material to be measured.
（5）Waste water material to be measured is added above-mentioned（3）In obtained mixed solution；Excited with 360nm excitation source,
Fluorescent emission intensity of the Detection wavelength in 620nm and 665nm；Calculate 665nm/620nm fluorescence intensities ratio, and with it is above-mentioned
（4）Resulting standard curve reference, i.e., the 665nm/620nm obtained test sample ratio are brought into calibration curve equation
In, by can be calculated the concentration of heavy metal in waste water material to be measured, by the ratio of obtained 665nm/620nm fluorescence intensities
Bring into standard curve, so as to calculate the concentration of heavy metal ions in wastewater to be measured.Utilize the metal obtained of this method
Ion detection is limited to：0.1nM, following result can be obtained, is illustrated in figure 3 check experiment, be existed in no heavy metal ion
In the case of, resulting fluorescence spectra, that is, there is no XL665 characteristic peaks, only EU3+The fluorescence spectra experiment of salt characteristic peak
Data.If Fig. 4 is wastewater sample testing experiment, in the presence of heavy metal ion, resulting fluorescence spectra, i.e.,
XL665 characteristic peaks and EU3+Existing fluorescence spectra while salt characteristic peak, red characteristic peak is XL665 feature in figure
Peak.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent change or modification that Spirit Essence is made, it should all be included within the scope of the present invention.
Claims (7)
- A kind of 1. detection method of high sensitivity heavy metal in water content, it is characterised in that：Comprise the following steps：Step 1. will contain Eu3+The europium cryptate of ion and 300nM 1-（3- dimethylamino-propyls）- 3- ethyls carbon two Imide liquor and 300nM N- hydroxy thiosuccinimide solution are stirred activation 30min and form the first activation mixing Liquid；50nM papains are stirred under conditions of 20 DEG C ~ 30 DEG C even by step 2. with the described first activation mixed liquor Connection reaction forms Eu3+The papain of salt modification, it is described to contain Eu3+The europium cryptate of ion and papain Molar ratio is 1：5, it is described to contain Eu3+The europium cryptate and 1- of ion（3- dimethylamino-propyls）- 3- ethyls carbon two is sub- The molar ratio of amine and N- hydroxy thiosuccinimides is 1：2 ~ 5, the Eu3+The papain of salt modification is through bag filter mistake Filter obtains Eu after purification3+The papain of salt modification；Step 3. is by fluorescent dye XL665 and 300nM 1-（3- dimethylamino-propyls）- 3- ethyl carbodiimides solution and 300nM N- hydroxy thiosuccinimide solution is stirred activation 30min and forms the second activation mixed liquor；50nM papains are stirred under conditions of 20 DEG C ~ 30 DEG C even by step 4. with the described second activation mixed liquor Connection reaction forms the papain of fluorescent dye XL665 modifications, the fluorescent dye XL665 and papain in step 4 Molar ratio be 1：5, the fluorescent dye XL665 and 1-（3- dimethylamino-propyls）- 3- ethyl carbodiimides and N- hydroxyls The molar ratio of thiosuccimide is 1：2~5；Step 5. is by the Eu3+The papain of salt modification is sufficiently mixed with the fluorescent dye XL665 papains modified Form fluoroscopic examination liquid, the Eu3+The papain that the papain of salt modification is modified with fluorescent dye XL665 is according to 1： 1 mol ratio is sufficiently mixed；Step 6. the fluoroscopic examination liquid is added after the aqueous solution to be detected excited through excitation source so as to detecting in 620nm and The fluorescent emission intensity of 665nm wavelength, and calculate 665nm fluorescent emission intensities and treated with 620nm fluorescent emission intensity ratios Survey liquid fluorescence ratio；Step 7. is by prepare liquid fluorescence ratio and standard fluorescence curve comparison so as to obtaining heavy metal ion in the aqueous solution to be detected Concentration, the standard fluorescence curve for based on several known heavy metal concentration standard liquid and the fluoroscopic examination liquid obtain The fluorescence curve that the liquid fluorescence ratio obtained calibrates.
- 2. according to the method for claim 1, it is characterised in that：The papain of the modifications of XL665 described in step 4 is through saturating Analyse the papain that bag filtering obtains XL665 modifications after purification.
- 3. according to the method for claim 1, it is characterised in that：The heavy metal includes Hg2+、Cu2+、Pb2+。
- 4. according to the method for claim 1, it is characterised in that：The stir speed (S.S.) of step 1 ~ 4 is 300rpm.
- 5. according to the method for claim 1, it is characterised in that：Optical source wavelength caused by excitation source is in the step 6 360nm。
- 6. according to the method for claim 1, it is characterised in that：The time of coupling reaction is 2h in the step 2, step 4.
- 7. according to the method for claim 1, it is characterised in that：The temperature of coupling reaction is 25 in the step 2, step 4 ℃。
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| US6689574B1 (en) * | 1997-10-07 | 2004-02-10 | Merck & Co., Inc. | Assays for nuclear receptor agonists and antagonists using fluorescence resonance energy transfer |
| CN102007395A (en) * | 2008-04-17 | 2011-04-06 | 凯杰博登湖有限公司 | Fluorescence standard, and the use thereof |
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| US7994274B2 (en) * | 2003-09-02 | 2011-08-09 | I.S.T. (Ma) Corporation | Two-stage cure polyimide oligomers |
| EP1810008A4 (en) * | 2004-10-15 | 2008-09-10 | Signal Pharm Llc | P27 ubiquitination assay and methods of use |
| DE602007010459D1 (en) * | 2007-09-04 | 2010-12-23 | Inst Nat Sante Rech Med | Use of compounds that prevent EF-Tu-Nucleolin interaction for the prevention or treatment of tularemia |
| US20120202702A1 (en) * | 2011-02-07 | 2012-08-09 | The Regents Of The University Of California | Detection of low concentration biological agents |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6689574B1 (en) * | 1997-10-07 | 2004-02-10 | Merck & Co., Inc. | Assays for nuclear receptor agonists and antagonists using fluorescence resonance energy transfer |
| CN102007395A (en) * | 2008-04-17 | 2011-04-06 | 凯杰博登湖有限公司 | Fluorescence standard, and the use thereof |
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| Modulation of Luminescence Intensity of Lanthanide Complexes by Photoinduced Electron Transfer and Its Application to a Long-Lived Protease Probe;Takuya Terai 等;《J.AM.CHEM.SOC》;20060506;第128卷(第21期);6938-6946 * |
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| 重金属检测方法的研究进展;姚振兴 等;《分析测试技术与仪器》;20110331;第17卷(第1期);29-35 * |
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Effective date of registration: 20190617 Address after: 215000 Chengyang International Science and Technology Pioneer Park, Xiangcheng Economic Development Zone, Suzhou, Jiangsu Province Patentee after: Ord Shinco (Suzhou) Medical Technology Co Ltd Address before: 215513 Jiangsu science and Technology Development Zone, Suzhou four Changshu Road 11 Chuang Chuang 201 Co-patentee before: Yang Xiaodong Patentee before: Liu Xiaolong Co-patentee before: Zhang Yun |