CN107290412B - A method of the electro-chemistry immunity based on ZnTCPP@MOF detects Microcystin - Google Patents
A method of the electro-chemistry immunity based on ZnTCPP@MOF detects Microcystin Download PDFInfo
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Abstract
The method for the electro-chemistry immunity detection Microcystin that the invention discloses a kind of based on ZnTCPP@MOF.The method modifies electrode with the Metal-organic frame ZnTCPP@MOF of porphyrin functionalization, and increase the stability of ZnTCPP@MOF on the electrode using ammonium bromide and tetraoctyl ammonium bromide, again by the way that microcapsule phycotoxin MC-LR antigen and monoclonal antibody is added dropwise, assembling forms electrochemical immunosensor.Electrochemical immunosensor made from the method for the present invention can be realized high sensitivity and the high specific detection of microcapsule phycotoxin MC-LR, the electrochemiluminescence signal of generation is stablized, it is low to the Monitoring lower-cut of microcapsule phycotoxin MC-LR, there is application prospect in biology and environment Microcystin detection field.
Description
Technical field
The invention belongs to electrochemical sensing technical fields, and in particular to a kind of electro-chemistry immunity inspection based on ZnTCPP@MOF
The method for surveying Microcystin.
Background technique
For a long time, water eutrophication and cyanobacterial bloom phenomenon frequently occur, and cause Microcystins in Water (MCs)
Pollution get worse.Microcapsule phycotoxin MC-LR has high risks effect, world health group to aquatile and human health
Being woven in and defining the safety limit of MC-LR in drinking water in " water hygiene benchmark " (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 carbon nanotube gold composite membrane in glassy carbon electrode surface, using MC-LR and antibody it
Between specific recognition effect building " sandwich " interlayer structure immunoassay formats, 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 there are higher costs for this method, and the range of linearity is narrow and detection limit is lower
The shortcomings that (the carbon nanotube/nano gold composite membrane electrochemical immunosensor such as Zhang Xinai for Microcystin detection study
[J] analytical chemistry, 2014,42.).Zhang Jinguo et al. is with the Microcystin (MCLR-HRP) of horseradish peroxidase
Marker, the immunoassay formats based on direct competitive construct MC-LR Amperometric Immunosensor, the linear inspection to MC-LR
Survey range is 0.79~12.9 μ g/L, and detection is limited to 0.38 μ g/L, however this method is complex for operation step, and the range of linearity is narrow, and
Detection limit is low, and (such as Zhang Jinguo are based on Fe3O4The Microcystin immune sensing of@Au magnetic nano-particle modification screen printing electrode
Device studies [J] analytical chemistry, 2013,41 (9): 1353-1358.).Therefore, a kind of simple cheap, quick and convenient is designed, it is sensitive
The better MC-LR detection method of property is of great significance.
Summary of the invention
It is narrow at high cost present in existing microcystic toxins checking method, the range of linearity and detection limit low is asked
Topic, the present invention provides a kind of electro-chemistry immunities simple, quick, at low cost based on ZnTCPP@MOF to detect Microcystin
Method.
The technical solution of the present invention is as follows:
A method of the electro-chemistry immunity based on ZnTCPP@MOF detects Microcystin, the specific steps are as follows:
Step 1, trimesic acid and zinc protoporphyrin the preparation of ZnTCPP@MOF: are added to isometric dehydrated alcohol and N, N-
Cu (NO is added to being uniformly dispersed in the in the mixed solvent of dimethylformamide (DMF), stirring3)2·3H2O solution, after mixing
It is placed at 60~120 DEG C and carries out hydro-thermal reaction, after reaction, be cooled to room temperature, be centrifuged, discard supernatant liquid, vacuum drying is
Obtain zinc protoporphyrin functional metal organic framework materials ZnTCPP@MOF；
Step 2, sensor assembles: pressing zinc protoporphyrin functional metal organic framework ZnTCPP@MOF and TOAB (four octyls
Ammonium bromide) mass ratio be 1:1, ZnTCPP@MOF and TOAB are dissolved in toluene, mixed solution is added drop-wise to clean electrode
Surface, it is dry under room temperature, n-hydroxysuccinimide/1- (3- dimethylamino-propyl) -3- ethyl carbon that molar ratio is 4:1 is added dropwise
The aqueous solution of diimmonium salt hydrochlorate (EDC/NHS) carries out activated carboxylic to frame object, and Microcystin to be detected is added dropwise in elution
LR is added dropwise microcapsule algae toxin resistant LR monoclonal antibody after incubating elution, is immunoreacted, incubates elution, i.e. assembling obtains electricity
Chemo-immunity sensor；
Step 3, electrochemiluminescdetection detection: being to electrode with platinum electrode, Ag/AgCl electrode is reference electrode, step 2
In electrode be working electrode, with contain 0.1M KNO30.1M, the PBS of pH 7.4 is electrolyte, detect ECL signal strength,
According to the linear relationship of the concentration of microcysin LR and ECL signal, the concentration of microcysin LR to be detected is calculated.
Preferably, in step 1, the hydro-thermal reaction time is 6~12h；The revolving speed of centrifugation is 9000r/min, centrifugation
Time is 10~20min；Vacuum drying temperature be 60~80 DEG C, drying time be 12~for 24 hours.
Preferably, in step 2, incubation conditions are to incubate 1h at 37 DEG C.
Preferably, in step 3, the electrogenerated chemiluminescence parameter are as follows: photomultiplier tube bias voltage is 1kV, amplification
Series is 3, and scanning potential range is -1.7~-0.5V, sweep speed 100mVs-1。
Compared with prior art, the present invention its remarkable advantage is as follows:
(1) ZnTCPP is fitted in the metal organic frame with porous structure and functionalization material has been prepared by the present invention
Expect ZnTCPP@MOF, which combines the photism of ZnTCPP and the bigger serface of metal framework material, abundant with antigen
Effect, has better electrochemical luminescence signals, and detection sensitivity is higher；
(2) present invention carries out signal transmitting using antigen and antibody direct immunization, and preparation step is simple and fast, operation side
Just, cost is relatively low, and the sensor of building is 0.1 μ of μ g/L~20 g/L to the linear detection range of microcysin LR, minimum
Detection is limited up to 0.06 μ g/L.
Detailed description of the invention
Fig. 1 is 1 mesoporphyrin functional metal organic framework materials ZnTCPP@MOF synthesis flow schematic diagram of embodiment.
Fig. 2 is the SEM of ZnTCPP@MOF (A) and HKUST-1 (Cu) (B) figure in embodiment 1.
Fig. 3 is the XRD spectrum (A) and infrared spectrogram of ZnTCPP@MOF (a) and HKUST-1 (Cu) (b) in embodiment 1
(B)。
Fig. 4 is the ECL signal relation figure (A) of TOAB mass and ZnTCPP@MOF in embodiment 2, and wherein m (TOAB) is indicated
Quality in 1mL 10mg/mL ZnTCPP@MOF toluene solution；(B) the ECL signal of ZnTCPP@MOF under 10mg TOAB is 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 graph and its linear diagram that sensor detects microcysin LR in embodiment 4.
Fig. 8 is sensor in embodiment 5 to NO3-, Ca2+, Mg2+, Fe3+With MC-RR interference--free experiments result figure.
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described.
Embodiment 1
The preparation method of porphyrin functional metal organic framework materials ZnTCPP@MOF, can refer to document [Porphyrin-
Encapsulated Metal-Organic Frameworks as Mimetic Catalysts for
Electrochemical DNA Sensing via Allosteric Switch of Hairpin DNA] it is prepared, have
Steps are as follows for body:
(1) 0.5g trimesic acid (H3BTC) and 30mg zinc protoporphyrin (ZnTCPP), it is added to 15ml 1:1 (V:V) anhydrous second
In the mixed liquor of alcohol and DMF, then again with 7.5ml Cu (NO3)2·3H2The aqueous solution of O (1.04g) mixes, by above-mentioned mixed liquor
Ultrasonic 20min makes its sufficiently homogeneous dispersion；
(2) mixed liquor is divided in the polytetrafluoroethyltank tank of 50ml and is sealed with autoclave, reaction kettle is put into
In electric heating constant-temperature blowing drying box, it is cooled to room temperature after heating 7h at 60 DEG C.
(3) cooling mixed liquid in step (2) is centrifuged 10min under the revolving speed of 9000r/min, after filtering off supernatant,
Precipitating particle is dissolved with dehydrated alcohol, centrifuge washing sedimented particle under the same terms is collected after continuously washing 3 times and obtains precipitating
Grain moves into vacuum oven and is dried in vacuo 12h at 60 DEG C, that is, the metal-organic framework material of porphyrin functionalization is prepared
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 figure
Material HKUST-1 (Cu) (Fig. 2 B) and ZnTCPP@MOF (Fig. 2A) has typical octoploids structure and crystal structure, explanation
Zinc protoporphyrin and the octahedral crystal structure for having not been changed prototype frame material HKUST-1 (Cu).Analyze XRD spectrum (Fig. 3 A) it is found that
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 sample,
Corresponding to (222) in octahedra crystalline structure standard card (JCPDF card number: 36-1452), (400), (331), (333),
(420) and (442) crystal face zinc protoporphyrin functional metal organic framework materials are further demonstrated, as 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 the peak as caused by the bending vibration of the c h bond on ZnTCPP pyrrole ring, illustrates that ZnTCPP has successfully modified metal frame
Frame object HKUST-1 (Cu) is to obtain functional metal frame object material ZnTCPP@MOF.
Embodiment 2
The toluene that the TOAB of 1mg, 5mg, 10mg, 15mg and 20mg are dissolved in 1mL 10mg/mLZnTCPP@MOF respectively is molten
In liquid, is taken in the above-mentioned solution modification to glass-carbon electrode of 20 μ L respectively, place drying under room temperature, be to electrode, Ag/ with platinum electrode
AgCl electrode is 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 strength.Electrogenerated chemiluminescence system parameter setting: photomultiplier tube bias voltage is
1kV, number of stages of amplification 3, scanning potential range are set as -1.7~-0.5V, sweep speed 100mVs-1.Testing result is such as
Shown in Fig. 4 (A), when TOAB dosage is very few, stability is inadequate on the electrode by ZnTCPP@MOF, is easy to fall off, and dosage is excessive
When, TOAB is blocked up in electrode surface film forming, can hinder electron transmission, weakens ECL signal, is 10mg (27mM) dosage in TOAB
Under, the ECL signal of ZnTCPP@MOF (10mg/ml) is best, and when Fig. 4 (B) corresponds to 10mg TOAB, ZnTCPP@MOF's shines
Signal and time relationship, ECL signal is strong and stability is more preferable, thus select mass ratio 1:1 for TOAB and ZnTCPP@MOF most
Excellent proportion.
Embodiment 3
MC-LR electrochemical immunosensor 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 surface is modified, at room temperature naturally dry, ZnTCPP@MOF (TOAB)/GCE electrode is made；In ZnTCPP@MOF
(TOAB) mixed aqueous solution of 20 μ L 400mM EDC and 100mM NHS is added dropwise on/GCE electrode, to Metal-organic frame
ZnTCPP@MOF carries out activated carboxylic, after reacting 30min at room temperature, elutes electrode surface with the PBS solution of 0.01M PH 7.4,
Then 20 μ L antigen MC-LR are modified on the electrode, are placed in after being incubated for 1h in 37 DEG C of incubate box, elute electrode table with PBS solution
Face removes excessive MC-LR, obtains MC-LR/ZnTCPP@MOF (TOAB)/GCE；Finally in modified electrode MC-LR/
20 μ L, 10 μ g/mL monoclone antibody against MC-LR (anti-MC-LR), 37 DEG C of incubations are added dropwise on ZnTCPP@MOF (TOAB)/GCE
After being incubated for 1h in case, electrode surface is eluted with the PBS solution of PH 7.4, electrode anti-MC-LR/MC-LR/ZnTCPP@is made
MOF (TOAB)/GCE, MC-LR electrochemical immunosensor are completed.
Electrochemical AC impedance (EIS) is commonly used for the characterization of electrode modification process interface variation, and Fig. 6 indicates electrode modification
Impedance variations situation in the process.Curve a and curve b respectively indicates bare glassy carbon electrode bare GCE and has modified ZnTCPP@MOF's
The AC impedance figure of electrode ZnTCPP@MOF/GCE, it can be seen that AC impedance variation is little, this is because ZnTCPP@MOF
Stability is bad on the electrode, is easy to fall off in electrolyte.Ammonium bromide and tetraoctyl ammonium bromide (TOAB) can increase ZnTCPP@MOF and exist
Stability on electrode.Curve c and curve d respectively indicates the electrode TOAB/GCE for having modified TOAB and electrode ZnTCPP@MOF
(TOAB)/GCE AC impedance figure, it can be seen that AC impedance is significantly increased compared to bare electrode, and curve d is greater than curve c
Impedance value, illustrate that ZnTCPP@MOF has successfully been fixed on electrode by TOAB.Curve e indicates to combine the electrode MC- of MC-LR
LR/ZnTCPP@MOF (TOAB)/GCE AC impedance figure, curve f indicate 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 obviously 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, has 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 detection microcysin LR, and detection process is as follows:
Configuration concentration gradient is that the MC-LR standard of 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 are molten
Liquid assembles MC-LR immune sensing electrode according to embodiment 3, is to electrode with platinum electrode, and Ag/AgCl electrode is 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 strength.Electrogenerated chemiluminescence system parameter setting: photomultiplier tube bias voltage is
1kV, number of stages of amplification 3, scanning potential range are set as -1.7~-0.5V, sweep speed 100mVs-1.
As Fig. 7 A indicate 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 illustrates antigen MC-LR concentration and preferable linear relationship is presented in ECL signal, and linear detection range is 0.1 μ g/L
~20 μ g/L, Monitoring lower-cut reach 0.06 μ g/L, illustrate that the ECL electrochemical immunosensor can be realized to microcysin LR
Highly sensitive detection.
Embodiment 5
Configuration concentration is the MC-LR standard solution of 5 μ g/L, is separately added into 1000 times of NO3-, Ca2+, Mg2+, Fe3+With 10 times
MC-RR as interfering substance, according to 4 step of embodiment, detect ECL signal.Testing result is as shown in figure 8, interfering substance pair
Sensor detects the ECL signal of MC-LR substantially without influence, shows that the sensor has preferable selectivity to MC-LR.
Claims (3)
1. a kind of method of the electro-chemistry immunity detection Microcystin based on ZnTCPP@MOF, which is characterized in that specific steps
It is as follows:
Step 1, trimesic acid and zinc protoporphyrin the preparation of ZnTCPP@MOF: are added to isometric dehydrated alcohol and N, N- diformazan
Cu (NO is added to being uniformly dispersed in the in the mixed solvent of base formamide, stirring3)2·3H2O solution, be uniformly mixed and be placed on 60~
120 DEG C of progress hydro-thermal reactions are cooled to room temperature after reaction, centrifugation, discard supernatant liquid, and vacuum drying obtains zinc protoporphyrin
Functional metal organic framework materials ZnTCPP@MOF；
Step 2, sensor assembles: by the matter of zinc protoporphyrin functional metal organic framework ZnTCPP@MOF and ammonium bromide and tetraoctyl ammonium bromide
ZnTCPP@MOF and ammonium bromide and tetraoctyl ammonium bromide are dissolved in toluene than being 1:1, mixed solution are added drop-wise to clean electrode table by amount
Face, dry under room temperature, the aqueous solution that the EDC/NHS that molar ratio is 4:1 is added dropwise carries out activated carboxylic to frame object, elutes, and is added dropwise
Microcysin LR to be detected is added dropwise microcapsule algae toxin resistant LR monoclonal antibody after incubating elution, is immunoreacted, incubated
Elution, i.e. assembling obtain electrochemical immunosensor；
Step 3, electrochemiluminescdetection detection: being to electrode with platinum electrode, and Ag/AgCl electrode is reference electrode, in step 2
Electrode is working electrode, to contain 0.1M KNO30.1M, the PBS of pH 7.4 is electrolyte, detect ECL signal strength, according to
The concentration of microcysin LR and the linear relationship of ECL signal, are calculated the concentration of microcysin LR to be detected, described
Electrogenerated chemiluminescence parameter are as follows: photomultiplier tube bias voltage be 1kV, number of stages of amplification 3, scanning potential range be -1.7
~-0.5V, sweep speed 100mVs-1。
2. the method according to claim 1, wherein the hydro-thermal reaction time is 6~12h in step 1；
The revolving 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~for 24 hours.
3. the method according to claim 1, wherein incubation conditions are to incubate 1h at 37 DEG C in step 2.
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| 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 |
| CN115181297B (en) * | 2022-06-08 | 2023-05-26 | 中国地质大学（武汉） | AlTCPP@MOF membrane based on porous alumina nano channel and preparation method and application thereof |
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