CN104181216A - Method for detecting acrylamide by sol-gel molecular imprinting electrochemical sensor based on nano material composite - Google Patents
Method for detecting acrylamide by sol-gel molecular imprinting electrochemical sensor based on nano material composite Download PDFInfo
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- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 title claims abstract description 47
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 13
- 239000002131 composite material Substances 0.000 title 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 36
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010931 gold Substances 0.000 claims abstract description 12
- 229910052737 gold Inorganic materials 0.000 claims abstract description 12
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- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000004070 electrodeposition Methods 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000006166 lysate Substances 0.000 claims description 4
- 229960003151 mercaptamine Drugs 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
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- 239000001117 sulphuric acid Substances 0.000 claims description 2
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- 239000002253 acid Substances 0.000 claims 3
- 238000001514 detection method Methods 0.000 abstract description 15
- 235000013305 food Nutrition 0.000 abstract description 13
- 238000011084 recovery Methods 0.000 abstract description 8
- 235000013606 potato chips Nutrition 0.000 abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 229910021397 glassy carbon Inorganic materials 0.000 abstract 2
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 238000002203 pretreatment Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001903 differential pulse voltammetry Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229960001230 asparagine Drugs 0.000 description 2
- 235000009582 asparagine Nutrition 0.000 description 2
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- 230000035945 sensitivity Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 2
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- 210000005036 nerve Anatomy 0.000 description 1
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Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
A method for detecting acrylamide by a sol-gel molecular imprinting electrochemical sensor based on a nano material compound comprises the steps of covering a compound of a carbon nano tube, gold nano particles and chitosan on the surface of a glassy carbon electrode, placing the glassy carbon electrode in a sol-gel solution containing template molecules, functional monomers and a cross-linking agent for electrochemical deposition, removing the template molecules after reaction is finished, and directly detecting the acrylamide in a sample by the obtained molecular imprinting electrochemical sensor. The carbon nano tube, the gold nano particles and the chitosan compound is prepared by modifying-COOH on the surface of the carbon nano tube, then carrying-SH on the modified-COOH, forming a stable compound by the gold nano particles and the carbon nano tube by utilizing the strong chemical action between the nano gold and the-SH, and then mixing the obtained compound with the chitosan. The method is simple, the sample pretreatment operation is simple, the detection speed is high, and the cost is low. In addition, the method has good selectivity and reproducibility, the recovery rate meets the requirement, acrylamide in fried foods such as potato chips and the like can be directly detected, and the method has important practical application value.
Description
Technical field
The present invention relates to detection and the electrochemical sensor field of food objectionable constituent, concrete relate to a kind of electrochemical sensor method that detects the collosol and gel molecular engram of acrylamide.
Background technology
Acrylamide (acrylamide, AM) is a kind of white crystalline material, the organic solvents such as stable under room temperature, soluble in water, methyl alcohol, ethanol, acetone, chloroform.AM has overt toxicity to human body, can cause the infringement of nerve system of human body.Zoopery and In vitro cell experiment all prove that AM can cause the generation of inhereditary material change and cancer.AMBei international cancer research institution (IARC) classifies 2A class carcinogenic substance (II A) as.
In April, 2002, in food, find first AM, particularly abundant in the high-temperature processed food that is rich in carbohydrates that the French fries of take are representative.Research shows, the AM in food is mainly because the asparagine in potato and cereal preparation raw material is generating after high-temperature cooking by Maillard reaction.2005, the risk assessment of system was carried out in the 64th meeting of WHO and the FAO food additives joint specialist council (JECFA) to AM, and warns the AM in public attention food, appealed to take measures to reduce AM content in food, to guarantee food security.China classifies the detection of Acrylamide in Foods as " 15 " national major scientific and technological project " food security gordian technique " problem, and Ministry of Public Health's food security plan also distributes investigation as an important content using AM in the foundation of the detection method of Acrylamide in Foods and China's food.
At present, the detection of Acrylamide in Foods content is mainly the modern chromatographic technique (GC of application, LC) etc. connect with mass spectroscopy (MS), as methods such as liquid-matter coupling method (LC-MS), gas-matter coupling method (GC-MS), liquid chromatography-tandem mass spectrometry analytic approachs (LC-MS/MS).Those methods are respectively having length aspect analysis time, cost and popularization, but sample pre-treatments more complicated, complex operation, detection time is long, and cost is high, and these analytical approach instrument and equipments are valuable, need professional to operate.
Summary of the invention
The object of the invention is, the sample pre-treatments existing in detection method for current existing Acrylamide in Foods is complicated, complex operation, the problem that detection time is long, cost is high, provide a kind of collosol and gel molecular imprinting electrochemical sensor based on nano material compound to detect the method for acrylamide, the method has good sensitivity, specificity, reappearance and the recovery, can be used for the detection of acrylamide in actual food product sample.
In order to achieve the above object, the technical solution used in the present invention is: a kind of collosol and gel molecular imprinting electrochemical sensor based on nano material compound detects the method for acrylamide, the method is to be modified with the glass-carbon electrode of the compound of carbon nano-tube, golden nanometer particle and shitosan, be placed in the sol gel solution that contains acrylamide and carry out electrochemical deposition, make molecular imprinting electrochemical sensor, with this sensor, the acrylamide in sample is directly detected.
The detailed process of above-mentioned collosol and gel molecular engram sensor direct-detection acrylamide is as follows, in conjunction with referring to Fig. 1:
1, the preparation of golden nanoparticle solution: press 1ml 1%HAuCl
4solution adds the ratio of 99ml ultrapure water, by HAuCl
4solution and ultrapure water mix, and at 150-250r/min, at 220 ℃, be heated to after boiling, then press 100ml0.01%HAuCl in magnetic stirring apparatus
4solution adds the ratio of 2.4ml1% citric acid three sodium solution, adds rapidly 1% citric acid three sodium solution, continues agitating heating 8-12min, until solution, by grey, after bright redness, stop heating, stir again 8-12min, be cooled to room temperature, just make required solution of gold nanoparticles.The solution of gold nanoparticles obtaining is placed in to 4 ℃ of refrigerators standby.
2, the activation of carbon nano-tube (MWNT): carbon nano-tube is placed in to nitration mixture (concentrated sulphuric acid and red fuming nitric acid (RFNA) by volume 3:1 mix) ultrasonic processing 3-4h (every 25mg carbon nano-tube need add 4ml nitration mixture), by the centrifugal (9000-11000r/min of ultrapure water for the carbon nano-tube solution obtaining, 4-6min) rinse to neutral, can obtain carboxylated carbon nano-tube (MWNT-COOH).
3, carbon nano-tube, the preparation of golden nanometer particle and chitosan complexes: at room temperature, in the 50mg/mLEDC that is first 1:1 in volume ratio by the MWNT after activation and the mixed liquor of 50mg/mL NHS, hatch 0.5-1.5h (carbon nano-tube after every 1mg activation adds 1ml mixed liquor), in cysteamine, hatch again 0.5-1.5h (carbon nano-tube after every 1mg activation adds 1ml cysteamine), make its surface with sulfydryl, with ultrapure water, rinse again, after being at room temperature dried, mix 0.5-1.5h (1mg adds 1ml solution of gold nanoparticles with the carbon nano-tube of sulfydryl) with above-mentioned solution of gold nanoparticles, obtain the compound of carbon nano-tube and golden nanometer particle.Then the ratio of 1:2 mixes with the compound of golden nanometer particle carbon nano-tube with 2.0wt% chitosan solution by volume.
4, the preparation of sol gel solution: the ratio that adds the tetrahydrofuran solution of 4-5mL in 0.4g-0.6g acrylamide, acrylamide is joined in tetrahydrofuran solution and dissolved, the ratio that adds 0.2mL function monomer 3-aminopropyl trimethoxysilane (APTMS) in 0.4g-0.6g acrylamide again in lysate adds 3-aminopropyl trimethoxysilane, with 250-350r/min stirring reaction 10-15min, the ratio that finally adds the ammoniacal liquor of 0.8mL crosslinking chemical tetraethoxysilane (TEOS) and 0.3mL 0.1mol/L in 0.4g-0.6g acrylamide in lysate adds tetraethoxysilane and ammoniacal liquor, with 250-350r/min stirring reaction 2h, obtain.
5, the structure of sensor: the compound of getting 10-15 μ L carbon nano-tube, gold nano and shitosan drips and is coated onto on glass-carbon electrode, drying at room temperature, the electrode of having modified is placed in to the sol gel solution making, under three-electrode system, utilizes cyclic voltammetry scanning 30 circles to carry out electro-deposition.The complete electrode of trace is placed under room temperature after dried overnight again with straight alcohol solution vibration wash-out, by the electrode after wash-out continue to be placed under room temperature dry after, be placed in the potassium ferricyanide that contains 5.0mM and the solution of the mixed liquor of potassium ferrocyanide and the 5mL 0.1M PBS (pH 7.4) of 0.1M KCl, adopt differential pulse voltammetry to carry out direct-detection to the acrylamide in sample.
The present invention be first by by carbon nano tube surface-COOH is through the method for amino coupled, make be connected with-SH of its surface, utilize gold nano and-extensive chemical effect between SH makes golden nanometer particle and carbon nano-tube form stable polymkeric substance, then the polymkeric substance obtaining and shitosan mixing are made to compound, then nano material is combined with molecular engram gel-sol technology.
Compared with prior art, advantage of the present invention is as follows:
1, the present invention is overlying on glass-carbon electrode surface by the compound of carbon nano-tube, golden nanometer particle and shitosan, utilize the dual strong electric conductivity of carbon nano-tube, golden nanometer particle, improved the susceptibility of electric current, utilize the adhesion of shitosan, strengthened the stability of collosol and gel molecular imprinting film on glass-carbon electrode, make this sensor both have good sensitivity and stronger stability, lowest detection is limited to 0.028 μ g/mL.
2, the present invention combines the compound of carbon nano-tube, golden nanometer particle and shitosan effectively with molecular engram sol-gel technique.The glass-carbon electrode surface of having modified carbon nano-tube, golden nanometer particle and chitosan complexes at this by molecular engram sol-gel technique, the molecular engram film of having prepared acrylamide carries out the detection of acrylamide.This technology not only operating conditions is gentle, and easily preparation, also can obviously improve the selectivity of molecular engram and the stability of material.In addition this sensor detection speed is fast, with low cost, and sample pre-treatments is simple to operate, has good specificity, reappearance and the recovery, directly the acrylamide in food is detected, and has important actual application value.
Accompanying drawing explanation
Fig. 1 is that sensor of the present invention builds schematic diagram.
Fig. 2 is specificity comparison diagram of the present invention.
Fig. 3 is typical curve and the linear relationship chart that the present invention detects acrylamide.
Embodiment
The sensor specificity experiment that embodiment 1 the present invention builds
By same concentration (1 μ g mL
-1) the molecular imprinting electrochemical sensor that makes in the present invention respectively of AM, acetone, asparagine, acetic acid on hatch 30min, then carry out differential pulse voltammetry measurement, contrast testing result.After getting acetone, propionic aldehyde, acetic acid and mixing with AM respectively, making its final concentration is 1 μ g mL
-1, on the molecular imprinting electrochemical sensor making in the present invention respectively, hatch 30min, then carry out differential pulse voltammetry measurement, contrast testing result.Result shows, the sensor that the present invention builds has good specificity, in conjunction with referring to Fig. 2.
Embodiment 2 detects the foundation of acrylamide typical curve
The sensor that the present invention is built is placed in the potassium ferricyanide that contains 5.0mM and the solution of the mixed liquor of potassium ferrocyanide and the 5mL 0.1M PBS (pH7.4) of 0.1M KCl, to the acrylamide of variable concentrations (0-15.0 μ g/mL, n=3) measure and measure, set up the typical curve that detects acrylamide, its range of linearity is 0.05-5 μ g mL
-1, lowest detection is limited to 0.028 μ g/mL, sees Fig. 3.
Embodiment 3 recovery testus
Potato chips sample: potato chips detect through high performance liquid chromatography, knows the content of its contained acrylamide, then gets appropriate acrylamide standard specimen and adds in sample, arrange 0.1,0.2,5 concentration of 1,2,4 μ g/mL, each concentration is established 3 repetitions, measures.
Sample pre-treatments: get 5g left and right potato chips sample and be placed in mortar and grind, to the acrylamide standard items that add different quality in sample, then sample is transferred in 50mL centrifuge tube, add the grease removal of 10mL normal hexane, Nitrogen evaporator dries up, then add the ultrasonic extraction of 20mL ultrapure water 15min, with the water system filtering membrane of 0.22 μ m, filter standby.
Experimental result is in Table 1, and the potato chips recovery experiment recovery is 81.4-94.8%, and the coefficient of variation is 2.06-4.28%, and the recovery is in allowed band.
Table 1 recovery experimental result
。
Claims (7)
1. a collosol and gel molecular imprinting electrochemical sensor based on nano material compound detects the method for acrylamide, it is characterized in that: the method is to be modified with the glass-carbon electrode of the compound of carbon nano-tube, golden nanometer particle and shitosan, be placed in the sol gel solution that contains acrylamide and carry out electrochemical deposition, make molecular imprinting electrochemical sensor, with this sensor, the acrylamide in sample is directly detected.
2. the collosol and gel molecular imprinting electrochemical sensor based on nano material compound as claimed in claim 1 detects the method for acrylamide, it is characterized in that: described compound is by the carbon nano-tube sulfhydrylation after activation, make its surface with sulfydryl, with ultrapure water, rinse again, after being at room temperature dried, in 1mg, with the carbon nano-tube of sulfydryl, add the ratio of 1ml solution of gold nanoparticles, carbon nano-tube with sulfydryl is mixed to 0.5-1.5h with solution of gold nanoparticles, obtain the compound of carbon nano-tube and golden nanometer particle; Finally by the compound of carbon nano-tube and golden nanometer particle and 2.0wt% chitosan solution by volume 1:2 mix, make.
3. the collosol and gel molecular imprinting electrochemical sensor based on nano material compound as claimed in claim 2 detects the method for acrylamide, it is characterized in that: described by activation after carbon nano-tube sulfhydrylation refer at room temperature, in the 50mg/mLEDC that is first 1:1 in volume ratio by the carbon nano-tube after activation and the mixed liquor of 50mg/mLNHS, hatch 0.5-1.5h, in cysteamine, hatch again 0.5-1.5h, wherein, the addition of mixed liquor is that the carbon nano-tube after every 1mg activation adds 1ml mixed liquor, half Guang by addition be that carbon nano-tube after every 1mg activation adds 1ml cysteamine.
4. the collosol and gel molecular imprinting electrochemical sensor based on nano material compound as claimed in claim 3 detects the method for acrylamide, it is characterized in that: the activation of described carbon nano-tube is that carbon nano-tube is placed in to volume ratio is the concentrated sulphuric acid of 3:1 and the ultrasonic processing of the acid mixture of red fuming nitric acid (RFNA) 3-4h, the carbon nano-tube solution obtaining is extremely neutral with ultrapure water centrifugal elutriation, obtain carboxylated carbon nano-tube, wherein, the addition of acid mixture is that every 25mg carbon nano-tube adds 4ml acid mixture.
5. the collosol and gel molecular imprinting electrochemical sensor based on nano material compound as claimed in claim 4 detects the method for acrylamide, it is characterized in that, described centrifugal rotational speed is 9000-11000r/min, and the time is 4-6min.
6. the collosol and gel molecular imprinting electrochemical sensor based on nano material compound as claimed in claim 2 detects the method for acrylamide, it is characterized in that, described golden nanoparticle solution refers to the 1%HAuCl by 1ml
4solution adds the ratio of 99ml ultrapure water, by HAuCl
4solution and ultrapure water mix, and at 150-250r/min, at 220 ℃, be heated to after boiling, then press 100ml0.01%HAuCl in magnetic stirring apparatus
4solution adds the ratio of 2.4ml1% citric acid three sodium solution, adds rapidly 1% citric acid three sodium solution, continues agitating heating 8-12min, stops heating, then stir 8-12min until solution by grey after bright redness, is cooled to room temperature.
7. the collosol and gel molecular imprinting electrochemical sensor based on nano material compound as claimed in claim 1 detects the method for acrylamide, it is characterized in that, the described sol gel solution that contains acrylamide is in the tetrahydrofuran solution of 4-5mL, to add the ratio of 0.4g-0.6g acrylamide, acrylamide is joined in tetrahydrofuran solution and dissolved, the ratio that adds 0.2mL function monomer 3-aminopropyl trimethoxysilane in 0.4g-0.6g acrylamide again in lysate adds 3-aminopropyl trimethoxysilane, with 250-350r/min, stir 10-15min, the last ratio that adds the ammoniacal liquor of 0.8mL crosslinking chemical tetraethoxysilane and 0.3mL 0.1mol/L in 0.4g-0.6g acrylamide in lysate adds tetraethoxysilane and ammoniacal liquor, with 250-350r/min, stir 2h, obtain.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106432645A (en) * | 2016-09-26 | 2017-02-22 | 山东省分析测试中心 | 'Mercapto-gold' modified silica-gel surface sudan molecularly imprinted material as well as preparation method and application thereof |
| CN108918613A (en) * | 2018-06-22 | 2018-11-30 | 江苏大学 | Based on gold nanoparticle/graphite alkene/chitosan trace cadmium ion electrochemical sensor, preparation method and its usage |
| CN109001279A (en) * | 2018-07-25 | 2018-12-14 | 江南大学 | A kind of preparation and application of glyphosate molecular engram electrode |
| CN109935378A (en) * | 2017-12-15 | 2019-06-25 | Tcl集团股份有限公司 | Composite nanometer particle and its preparation method and application |
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| CN113030208A (en) * | 2021-03-01 | 2021-06-25 | 广西壮族自治区农业科学院 | Indoleacetic acid porous molecularly imprinted sensor prepared by electrochemistry and application thereof |
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| WO2023197643A1 (en) * | 2022-04-15 | 2023-10-19 | 齐鲁工业大学 | Gene nanosensor, and preparation method therefor and use thereof |
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