CN107290412A - A kind of method that electro-chemistry immunity based on ZnTCPP@MOF detects Microcystin - Google Patents
A kind of method that electro-chemistry immunity based on ZnTCPP@MOF detects Microcystin Download PDFInfo
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Abstract
The invention discloses a kind of method that electro-chemistry immunity based on ZnTCPP@MOF detects Microcystin.Methods described is modified electrode with the Metal-organic frame ZnTCPP@MOF of porphyrin functionalization, and increase stability of the ZnTCPP@MOF on electrode using ammonium bromide and tetraoctyl ammonium bromide, again by the way that Microcystin MC LR antigens and monoclonal antibody is added dropwise, assembling forms electrochemical immunosensor.Electrochemical immunosensor made from the inventive method can realize Microcystin MC LR high sensitivity and high specific detection, the electrochemiluminescence signal of generation is stable, it is low to Microcystin MC LR Monitoring lower-cut, there is application prospect in biological and environment Microcystin detection field.
Description
Technical field
The invention belongs to electrochemical sensing technical field, and in particular to a kind of electro-chemistry immunity inspection based on ZnTCPP@MOF
The method for surveying Microcystin.
Background technology
For a long time, body eutrophication and blue-green alga bloom phenomenon frequently occur, and cause Microcystins in Water (MCs)
Pollution it is increasingly serious.Microcapsule phycotoxin MC-LR has high risks effect, world health group to aquatile and human health
It is woven in《Water hygiene benchmark》The safety limit that MC-LR in drinking water is defined in (2004 editions) is 1.0 μ g/L, therefore is drunk
The monitoring of MC-LR concentration is particularly important in water source.
Zhang Xinai et al. has modified the golden composite membrane of carbon nanotube in glassy carbon electrode surface, using MC-LR and antibody it
Between specific recognition effect build the immunoassay formats of " sandwich " interlayer structure, the linear detection range to MC-LR is
0.50~12.0 μ g/L, detection is limited to 0.30 μ g/L, but to there is cost higher for this method, and the range of linearity is narrow and test limit is relatively low
Shortcoming (detection that the such as Zhang Xinai carbon nanotube/nanos gold composite membrane electrochemical immunosensor is used for Microcystin is studied
[J] analytical chemistry, 2014,42.).Zhang Jinguo et al. is with the Microcystin (MCLR-HRP) of horseradish peroxidase
Label, the immunoassay formats based on direct competitive construct MC-LR Amperometric Immunosensors, the linear inspection to MC-LR
Survey scope is 0.79~12.9 μ g/L, detects and is limited to 0.38 μ g/L, but this method complex operation step, and the range of linearity is narrow, and
Test limit is low, and (such as Zhang Jinguo is based on Fe3O4@Au magnetic nano-particles modify the Microcystin immune sensing of screen printing electrode
Device studies [J] analytical chemistry, 2013,41 (9):1353-1358.).Therefore, design a kind of simple cheap, it is quick and convenient, it is sensitive
The more preferable MC-LR detection methods of property are significant.
The content of the invention
Asked for cost present in existing microcystic toxins checking method is high, the range of linearity is narrow and test limit is low
Topic, Microcystin is detected the invention provides a kind of low electro-chemistry immunity based on ZnTCPP@MOF of simple, quick, cost
Method.
The technical scheme is that：
A kind of method that electro-chemistry immunity based on ZnTCPP@MOF detects Microcystin, is comprised the following steps that：
Step 1, ZnTCPP@MOF preparation：Trimesic acid and zinc protoporphyrin are added to isometric absolute ethyl alcohol and N, N-
The in the mixed solvent of dimethylformamide (DMF), stirring adds Cu (NO to being uniformly dispersed3)2·3H2O solution, after being well mixed
It is placed at 60~120 DEG C and carries out hydro-thermal reaction, after reaction terminates, be cooled to normal temperature, centrifuge, abandoning supernatant, vacuum drying is
Obtain zinc protoporphyrin functional metal organic framework materials ZnTCPP@MOF；
Step 2, sensor is assembled：By zinc protoporphyrin functional metal organic framework ZnTCPP@MOF and TOAB (four octyl groups
Ammonium bromide) mass ratio be 1:1, ZnTCPP@MOF and TOAB are dissolved in toluene, mixed solution is added drop-wise to the electrode of cleaning
Dried under surface, normal temperature, it is 4 that mol ratio, which is added dropwise,:1 n-hydroxysuccinimide/1- (3- dimethylamino-propyls) -3- ethyl carbon
The aqueous solution of diimmonium salt hydrochlorate (EDC/NHS) carries out activated carboxylic to framework thing, and Microcystin to be detected is added dropwise in elution
LR, incubates and microcapsule algae toxin resistant LR monoclonal antibodies is added dropwise after elution, carries out immune response, incubates elution, i.e. assembling obtains electricity
Chemo-immunity sensor；
Step 3, electrochemiluminescdetection detection：Using platinum electrode as to electrode, Ag/AgCl electrodes are reference electrode, step 2
In electrode be working electrode, to contain 0.1M KNO30.1M, pH 7.4 PBS is electrolyte, detects ECL signal intensities,
According to the concentration of microcysin LR and the linear relationship of ECL signals, the concentration for obtaining microcysin LR to be detected is calculated.
Preferably, in step 1, described the hydro-thermal reaction time is 6~12h；The rotating speed of centrifugation is 9000r/min, centrifugation
Time is 10~20min；Vacuum drying temperature is 60~80 DEG C, and drying time is 12~24h.
Preferably, in step 2, incubation conditions be 37 DEG C at incubate 1h.
Preferably, in step 3, described electrogenerated chemiluminescence parameter is：Photomultiplier bias voltage is 1kV, amplification
Series is 3, and scanning potential range is -1.7~-0.5V, and sweep speed is 100mVs-1。
Compared with prior art, its remarkable advantage is as follows by the present invention：
(1) ZnTCPP is fitted in the metal organic frame with loose structure by the present invention has prepared functionalization material
Expect ZnTCPP@MOF, the material combines ZnTCPP photism and the bigger serface of metal framework material, abundant with antigen
Effect, with more preferable electrochemical luminescence signals, detection sensitivity is higher；
(2) present invention carries out signal transmission, preparation process simple and fast, operation side using antigen and antibody direct immunization
Just, cost is relatively low, and the sensor of structure is the μ g/L of 0.1 μ g/L~20 to the linear detection range of microcysin LR, and its is minimum
Test limit is up to 0.06 μ g/L.
Brief description of the drawings
Fig. 1 is the mesoporphyrin functional metal organic framework materials ZnTCPP@MOF synthesis flow schematic diagrames of embodiment 1.
Fig. 2 is the SEM figures of ZnTCPP@MOF (A) and HKUST-1 (Cu) (B) in embodiment 1.
XRD spectrum (A) and infrared spectrogram that Fig. 3 is ZnTCPP@MOF (a) and HKUST-1 (Cu) (b) in embodiment 1
(B)。
Fig. 4 is TOAB mass and ZnTCPP@MOF ECL signal relations figure (A) in embodiment 2, and wherein m (TOAB) is represented
Quality in 1mL 10mg/mL ZnTCPP@MOF toluene solutions；(B) the ECL signals of ZnTCPP@MOF under 10mg TOAB are corresponded to
With time chart.
Fig. 5 is the assembling schematic diagram of electrochemical immunosensor in embodiment 3.
Fig. 6 is electrode assembling process electrochemical AC impedance variation diagram in embodiment 3.
Fig. 7 is the ECL signal graphs and its linear diagram of sensor detection microcysin LR in embodiment 4.
Fig. 8 is sensor in embodiment 5 to NO3-, Ca2+, Mg2+, Fe3+With MC-RR interference--free experiments result figures.
Embodiment
With reference to embodiment and accompanying drawing, the invention will be further described.
Embodiment 1
Porphyrin functional metal organic framework materials ZnTCPP@MOF preparation method, refers to document【Porphyrin-
Encapsulated Metal-Organic Frameworks as Mimetic Catalysts for
Electrochemical DNA Sensing via Allosteric Switch of Hairpin DNA】Prepare, have
Body step is as follows：
(1) 0.5g trimesic acids (H3BTC) and 30mg zinc protoporphyrins (ZnTCPP), it is added to 15ml 1：1(V：V) anhydrous second
In alcohol and DMF mixed liquor, then again with 7.5ml Cu (NO3)2·3H2O (1.04g) aqueous solution mixing, by above-mentioned mixed liquor
Ultrasonic 20min, makes it fully homogeneous scattered；
(2) mixed liquor is divided in 50ml polytetrafluoroethyltank tank and sealed with autoclave, reactor is put into
In electric heating constant-temperature blowing drying box, normal temperature is cooled to after heating 7h at 60 DEG C.
(3) cooling mixed liquid in step (2) is centrifuged into 10min under 9000r/min rotating speed, filtered off after supernatant,
Centrifuge washing sedimented particle under particle, the same terms is precipitated with absolute ethyl alcohol dissolving, is collected after continuously washing 3 times and obtains precipitation
Grain, moves into vacuum drying chamber and is dried in vacuo 12h at 60 DEG C, that is, prepare the metal-organic framework material of porphyrin functionalization
ZnTCPP@MOF.Preparation process is as shown in Figure 1.
To porphyrin functional metal organic framework materials ZnTCPP@MOF and its prototype metal-organic framework material HKUST-1
(Cu) SEM, XRD and IR Characterization analysis are carried out, as a result as shown in Figure 2.The prototype metal organic frame it can be seen from SEM figures
Material HKUST-1 (Cu) (Fig. 2 B) and ZnTCPP@MOF (Fig. 2A) have typical octoploids structure and crystal structure, explanation
Zinc protoporphyrin does not change prototype frame material HKUST-1 (Cu) octahedral crystal structure.XRD spectrum (Fig. 3 A) is analyzed to understand,
There is diffraction maximum at 11.8,13.5,14.9,17.6,19.2,20.4 angles in HKUST-1 (Cu) and ZnTCPP@MOF samples,
Corresponding to octahedra crystalline structure standard card (JCPDF card numbers：(222) in 36-1452), (400), (331), (333),
(420) and (442) crystal face, further demonstrate zinc protoporphyrin functional metal organic framework materials is octahedra crystalline structure.By
Infrared spectrogram can be seen that ZnTCPP (Fig. 3 B (b)) and ZnTCPP@MOF (Fig. 3 B (a)) in 1000cm-1There is peak appearance, this
It is due to the peak produced by the flexural vibrations of c h bond on ZnTCPP pyrrole rings, illustrates that ZnTCPP has successfully modified metal frame
Frame thing HKUST-1 (Cu) is so as to obtain functional metal framework thing material ZnTCPP@MOF.
Embodiment 2
The toluene that 1mg, 5mg, 10mg, 15mg and 20mg TOAB are dissolved in into 1mL 10mg/mLZnTCPP@MOF respectively is molten
In liquid, take the above-mentioned solution modifications of 20 μ L to glass-carbon electrode respectively, drying is placed under normal temperature, using platinum electrode as to electrode, Ag/
AgCl electrodes are reference electrode, using the good electrode of above-mentioned modification as working electrode, to contain 0.1M KNO30.1M pH
7.4PBS is electrolyte, detects ECL signal intensities.Electrogenerated chemiluminescence system parameter setting：Photomultiplier bias voltage is
1kV, number of stages of amplification is 3, and scanning potential range is set to -1.7~-0.5V, and sweep speed is 100mVs-1.Testing result is such as
Shown in Fig. 4 (A), when TOAB consumptions are very few, ZnTCPP@MOF not enough, easily come off in electrode upward stability, and consumption is excessive
When, TOAB is blocked up in electrode surface film forming, can hinder electron transmission, weakens ECL signals, is 10mg (27mM) consumption in TOAB
Under, preferably, when Fig. 4 (B) corresponds to 10mg TOAB, ZnTCPP@MOF's is luminous for ZnTCPP@MOF (10mg/ml) ECL signals
Signal and time relationship, ECL signals are strong and stability is more preferable, so selection mass ratio 1:1 be TOAB and ZnTCPP@MOF most
Excellent proportioning.
Embodiment 3
MC-LR electrochemical immunosensors assembling process is as shown in figure 5, key step is as follows：
The toluene mixed solution of 20 μ L 10mg/mL ZnTCPP@MOF and 10mg/mL ammonium bromide and tetraoctyl ammonium bromides (TOAB) is dripped
GCE electrode surfaces are modified, are dried naturally at room temperature, ZnTCPP@MOF (TOAB)/GCE electrodes are made；In ZnTCPP@MOF
(TOAB) 20 μ L 400mM EDC and 100mM NHS mixed aqueous solution is added dropwise on/GCE electrodes, to Metal-organic frame
ZnTCPP@MOF carry out activated carboxylic, react at room temperature after 30min, and electrode surface is eluted with 0.01M PH 7.4 PBS solution,
Then 20 μ L antigen MC-LR are modified on electrode, is placed in being incubated after 1h in 37 DEG C of incubate box, electrode table is eluted with PBS solution
Face, removes excessive MC-LR, that is, MC-LR/ZnTCPP@MOF (TOAB)/GCE is made；Finally in modified electrode MC-LR/
The μ g/mL monoclone antibody against MC-LR (anti-MC-LR) of 20 μ L 10,37 DEG C of incubations are added dropwise on ZnTCPP@MOF (TOAB)/GCE
It is incubated in case after 1h, elutes electrode surface with PH 7.4 PBS solution, electrode anti-MC-LR/MC-LR/ZnTCPP@are made
MOF (TOAB)/GCE, MC-LR electrochemical immunosensors are to be completed.
Electrochemical AC impedance (EIS) is commonly used for the sign of electrode modification process interface change, and Fig. 6 represents electrode modification
During impedance variations situation.Curve a and curve b represent bare glassy carbon electrode bare GCE and have modified ZnTCPP@MOF's respectively
Electrode ZnTCPP MOF/GCE AC impedance figure, it can be seen that less, this is due to ZnTCPP MOF to AC impedance value changes
It is bad in electrode upward stability, easily it is shed in electrolyte.Ammonium bromide and tetraoctyl ammonium bromide (TOAB) can increase ZnTCPP@MOF and exist
Stability on electrode.Curve c and curve d represent to have modified TOAB electrode TOAB/GCE and electrode ZnTCPP@MOF respectively
(TOAB)/GCE AC impedance figure, it can be seen that AC impedance is significantly increased compared to bare electrode, and curve d is more than curve c
Impedance value, illustrate that ZnTCPP@MOF have successfully been fixed on electrode by TOAB.Curve e represents to combine MC-LR electrode MC-
LR/ZnTCPP@MOF (TOAB)/GCE AC impedance figure, curve f represents that monoclone antibody against MC-LR (anti-MC- is added dropwise
LR after), i.e. anti-MC-LR/MC-LR/ZnTCPP@MOF (TOAB)/GCE AC impedance figure, because antigen, antibody are not led
Electricity, hinders electron transmission, therefore curve e compares curve d with f, and AC impedance substantially increases, and AC impedance Z (f) ＞ Z
(e), illustrate that antigen and antibody occur immune response and forms immune complex, the compound is electroactive lower, with bigger impedance
Effect.The assembling process that can be seen that microcysin LR electrochemical immunosensor from impedance variations situation is successful.
Embodiment 4
Metal-organic framework material ZnTCPP@MOF can be applied to detect microcysin LR, and detection process is as follows：
Configuration concentration gradient is that 0.1 μ g/L, 1 μ g/L, 5 μ g/L, 10 μ g/L, 15 μ g/L and 20 μ g/L MC-LR standards are molten
Liquid, MC-LR immune sensing electrodes are assembled according to embodiment 3, and using platinum electrode as to electrode, Ag/AgCl electrodes are reference electrode,
Anti-MC-LR/MC-LR/ZnTCPP@MOF (TOAB)/GCE is as working electrode, with the 0.1M pH containing 0.1M KNO3
7.4PBS is electrolyte, detects ECL signal intensities.Electrogenerated chemiluminescence system parameter setting：Photomultiplier bias voltage is
1kV, number of stages of amplification is 3, and scanning potential range is set to -1.7~-0.5V, and sweep speed is 100mVs-1.
As Fig. 7 A represent blank and MC-LR concentration be respectively 0.1,1,5,10,15 and 20 μ g/L ECL intensity (by height to
It is low), Fig. 7 B illustrate that preferable linear relationship is presented with ECL signals in antigen MC-LR concentration, and its linear detection range is 0.1 μ g/L
~20 μ g/L, Monitoring lower-cut reaches 0.06 μ g/L, illustrates that the ECL electrochemical immunosensors can be realized to microcysin LR
Highly sensitive detection.
Embodiment 5
Configuration concentration is 5 μ g/L MC-LR standard liquids, is separately added into 1000 times of NO3-, Ca2+, Mg2+, Fe3+With 10 times
MC-RR as interfering material, according to the step of embodiment 4, detect ECL signals.Testing result is as shown in figure 8, interfering material pair
Sensor detection MC-LR ECL signals show that the sensor has preferable selectivity to MC-LR substantially without influence.
Claims (4)
1. a kind of method that electro-chemistry immunity based on ZnTCPP@MOF detects Microcystin, it is characterised in that specific steps
It is as follows：
Step 1, ZnTCPP@MOF preparation：Trimesic acid and zinc protoporphyrin are added to isometric absolute ethyl alcohol and N, N- diformazan
The in the mixed solvent of base formamide, stirring adds Cu (NO to being uniformly dispersed3)2·3H2O solution, it is well mixed after be placed in 60~
120 DEG C of progress hydro-thermal reactions, after reaction terminates, are cooled to normal temperature, centrifuge, abandoning supernatant, vacuum drying obtains zinc protoporphyrin
Functional metal organic framework materials ZnTCPP@MOF；
Step 2, sensor is assembled：By zinc protoporphyrin functional metal organic framework ZnTCPP@MOF and the matter of ammonium bromide and tetraoctyl ammonium bromide
Amount is than being 1:1, ZnTCPP@MOF and ammonium bromide and tetraoctyl ammonium bromide are dissolved in toluene, mixed solution is added drop-wise to the electrode table of cleaning
Dried under face, normal temperature, it is 4 that mol ratio, which is added dropwise,:The 1 EDC/NHS aqueous solution carries out activated carboxylic to framework thing, elutes, and is added dropwise
Microcysin LR to be detected, incubates and microcapsule algae toxin resistant LR monoclonal antibodies is added dropwise after elution, carries out immune response, incubates
Elution, i.e. assembling obtain electrochemical immunosensor；
Step 3, electrochemiluminescdetection detection：Using platinum electrode as to electrode, during Ag/AgCl electrodes are reference electrode, step 2
Electrode is working electrode, to contain 0.1M KNO30.1M, pH 7.4 PBS is electrolyte, detects ECL signal intensities, according to
The concentration of microcysin LR and the linear relationship of ECL signals, calculate the concentration for obtaining microcysin LR to be detected.
2. according to the method described in claim 1, it is characterised in that in step 1, described the hydro-thermal reaction time is 6~12h；
The rotating speed of centrifugation is 9000r/min, and centrifugation time is 10~20min；Vacuum drying temperature is 60~80 DEG C, and drying time is
12~24h.
3. according to the method described in claim 1, it is characterised in that in step 2, incubation conditions be 37 DEG C at incubate 1h.
4. according to the method described in claim 1, it is characterised in that in step 3, described electrogenerated chemiluminescence parameter is：Light
Electric multiplier tube bias voltage is 1kV, and number of stages of amplification is 3, and scanning potential range is -1.7~-0.5V, and sweep speed is 100mV
s-1。
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| CN108051491A (en) * | 2017-12-18 | 2018-05-18 | 重庆医科大学 | A kind of electrochemical immunosensor for being used to detect LAG-3 albumen |
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| CN110018144A (en) * | 2019-04-17 | 2019-07-16 | 南京理工大学 | Inorganic ions electrochemiluminescdetection detection method based on ZnTCPP@MOF |
| CN110018144B (en) * | 2019-04-17 | 2021-11-09 | 南京理工大学 | Inorganic ion electrochemiluminescence detection method based on ZnTCPP @ MOF |
| CN110724522A (en) * | 2019-10-27 | 2020-01-24 | 浙江理工大学 | Preparation method of tetramethoxyphenyl manganese porphyrin-Zn-MOF fluorescent material |
| CN113916953A (en) * | 2020-11-27 | 2022-01-11 | 青岛大学 | Two-dimensional porphyrin MOFs/TOAB modified electrode, preparation method and application |
| CN113916953B (en) * | 2020-11-27 | 2023-08-08 | 青岛大学 | Two-dimensional porphyrin MOFs/TOAB modified electrode and preparation method and application thereof |
| CN113663646A (en) * | 2021-07-19 | 2021-11-19 | 中国计量大学 | Preparation method and application of wide-spectrum specific antibody modified magnetic metal organic framework material |
| CN115181297A (en) * | 2022-06-08 | 2022-10-14 | 中国地质大学（武汉） | AlTCPP @ MOF membrane based on porous alumina nanochannel and preparation method and application thereof |
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