CN104181216B - 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 49
- 238000000034 method Methods 0.000 title claims abstract description 29
- 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
- 238000001514 detection method Methods 0.000 claims abstract description 22
- 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
- 239000002105 nanoparticle Substances 0.000 claims abstract description 11
- 229920001661 Chitosan Polymers 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims abstract description 5
- 238000004070 electrodeposition Methods 0.000 claims abstract description 4
- 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
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 9
- 239000012498 ultrapure water Substances 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 8
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 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
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 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
- 238000003756 stirring Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 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
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 3
- 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
- 229910021397 glassy carbon Inorganic materials 0.000 abstract description 4
- 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 4
- 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
- 238000005259 measurement 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
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- -1 potassium ferricyanide Chemical compound 0.000 description 2
- 239000000276 potassium ferrocyanide Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 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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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, particularly relate to a kind of electrochemical sensor method detecting the collosol and gel molecular engram of acrylamide.
Background technology
Acrylamide (acrylamide, AM) is a kind of white crystalline material, room-temperature stable, soluble in water, the organic solvent such as 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.AM is classified as 2A class carcinogenic substance (II A) by international cancer research institution (IARC).
In April, 2002, Late Cambrian AM in food is that being rich in the high-temperature processed food of carbohydrates of representative is particularly abundant with French fries.Research shows, the AM in food is mainly because the asparagine in potato and cereal preparation raw material is being generated after high-temperature cooking by Maillard reaction.2005, WHO and the FAO food additives joint specialist council (JECFA) the 64th meeting has carried out the risk assessment of system to AM, and warn the AM in public attention food, appeal to take measures to reduce AM content in food, to guarantee food security.The detection of Acrylamide in Foods is classified as " 15 " national major scientific and technological project " food security gordian technique " problem by China, Ministry of Public Health's food security plan also using AM Morbidity investigation in the foundation of the detection method of Acrylamide in Foods and China's food as an important content.
At present, modern chromatographic techniques (GC is mainly applied in the detection of Acrylamide in Foods content, etc. LC) connect with mass spectroscopy (MS), as methods such as liquid-mass chromatography method (LC-MS), gas chromatographymass spectrum (GC-MS), liquid chromatography-tandem mass spectrometry analytic approachs (LC-MS/MS).Those methods respectively have length in analysis time, cost and popularization, but sample pre-treatments more complicated, and 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 existed in detection method for current existing Acrylamide in Foods is complicated, complex operation, the problem that detection time is long, cost is high, there is provided 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 the glass-carbon electrode of the compound by being modified with carbon nano-tube, golden nanometer particle and shitosan, the sol gel solution be placed in containing acrylamide carries out electrochemical deposition, obtained molecular imprinting electrochemical sensor, directly detects the acrylamide in sample with this sensor.Wherein, containing adopting 3-aminopropyl trimethoxysilane as function monomer in the sol gel solution of acrylamide, tetraethoxysilane is as crosslinking chemical.
The detailed process of above-mentioned collosol and gel molecular engram sensor direct-detection acrylamide is as follows, in conjunction with see Fig. 1:
1, the preparation of golden nanoparticle solution: by 1ml 1%HAuCl
4solution adds the ratio of 99ml ultrapure water, by HAuCl
4solution and ultrapure water mixing, at 150-250r/min, at 220 DEG C, after magnetic stirring apparatus is heated to boiling, then press 100ml0.01%HAuCl
4solution adds the ratio of 2.4ml 1% citric acid three sodium solution, adds rapidly 1% citric acid three sodium solution, continues agitating heating 8-12min, heating is stopped after solution is by grey to bright redness, stir 8-12min again, be cooled to room temperature, just obtained required solution of gold nanoparticles.The solution of gold nanoparticles obtained is placed in 4 DEG C of refrigerators for subsequent use.
2, the activation of carbon nano-tube (MWNT): carbon nano-tube is placed in nitration mixture (the 3:1 mixing by volume of the concentrated sulphuric acid and red fuming nitric acid (RFNA)) ultrasonic process 3-4h (every 25mg carbon nano-tube need add 4ml nitration mixture), by the centrifugal (9000-11000r/min of carbon nano-tube solution ultrapure water obtained, 4-6min) rinse to neutral, carboxylated carbon nano-tube (MWNT-COOH) can be obtained.
3, carbon nano-tube, the preparation of golden nanometer particle and chitosan complexes: at room temperature, be first in the mixed liquor of 50mg/mLEDC and the 50mg/mL NHS of 1:1, hatch 0.5-1.5h (carbon nano-tube after every 1mg activation adds 1ml mixed liquor) in volume ratio by the MWNT after activation, 0.5-1.5h (carbon nano-tube after every 1mg activation adds 1ml cysteamine) is hatched again in cysteamine, make its surface with sulfydryl, use ultrapure water again, at room temperature mix 0.5-1.5h (1mg is with the carbon nano-tube of sulfydryl to add 1ml solution of gold nanoparticles) with above-mentioned solution of gold nanoparticles after drying, obtain the compound of carbon nano-tube and golden nanometer particle.Then carbon nano-tube mixes with 2.0wt% chitosan solution with the compound of golden nanometer particle by the ratio of 1:2 by volume.
4, the preparation of sol gel solution: the ratio adding the tetrahydrofuran solution of 4-5mL in 0.4g-0.6g acrylamide, acrylamide is joined in tetrahydrofuran solution and dissolves, the ratio adding 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 last ratio adding 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 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 modified is placed in obtained sol gel solution, under three-electrode system, utilizes cyclic voltammetry to scan 30 circles carry out electro-deposition.Straight alcohol solution vibration wash-out is used again after electrode complete for trace being placed in dry at room temperature over night, electrode after wash-out to be continued be placed under room temperature after drying, be placed in the solution of the potassium ferricyanide containing 5.0mM and 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 first passes through the method for carbon nano tube surface-COOH through amino coupled, its surface is made to be connected with-SH, the extensive chemical effect between gold nano and-SH is utilized to make golden nanometer particle and carbon nano-tube form stable polymkeric substance, then the polymkeric substance obtained and shitosan mixing are obtained 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 compound of carbon nano-tube, golden nanometer particle and shitosan is overlying on glassy carbon electrode surface by the present invention, utilize the dual strong electric conductivity of carbon nano-tube, golden nanometer particle, improve the susceptibility of electric current, utilize the adhesion of shitosan, enhance 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 compound of carbon nano-tube, golden nanometer particle and shitosan combines with molecular engram sol-gel technique by the present invention effectively.By the glassy carbon electrode surface that molecular engram sol-gel technique has modified carbon nano-tube, golden nanometer particle and chitosan complexes at this, the molecular engram film having prepared acrylamide carries out the detection of acrylamide.This technology not only operating conditions is gentle, easily prepares, also can significantly improve the selectivity of molecular engram and the stability of material.In addition this sensor detection speed is fast, and with low cost, sample pre-treatments is simple to operate, has good specificity, reappearance and the recovery, directly detects the acrylamide in food, 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 experiments that embodiment 1 the present invention builds
By same concentration (1 μ g mL
-1) the molecular imprinting electrochemical sensor that obtains in the present invention respectively of AM, acetone, asparagine, acetic acid on hatch 30min, then carry out differential pulse voltammetry measurement, contrast testing result.Get after acetone, propionic aldehyde, acetic acid mixes with AM respectively, make its final concentration be 1 μ g mL
-1, the molecular imprinting electrochemical sensor obtained in the present invention respectively carries out hatching 30min, then carries out differential pulse voltammetry measurement, contrast testing result.Result shows, the sensor that the present invention builds has good specificity, in conjunction with see Fig. 2.
Embodiment 2 detects the foundation of acrylamide typical curve
Sensor the present invention built is placed in the solution of the potassium ferricyanide containing 5.0mM and the mixed liquor of potassium ferrocyanide and the 5mL 0.1M PBS (pH7.4) of 0.1M KCl, to acrylamide (the 0-15.0 μ g/mL of variable concentrations, n=3) carry out measurement to measure, set up the typical curve detecting 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 testu
Potato chips sample: potato chips detect through high performance liquid chromatography, knows the content of acrylamide contained by it, then gets appropriate acrylamide standard specimen and adds in sample, arrange 0.1,0.2,1,2,4 μ g/mL, 5 concentration, each concentration establishes 3 repetitions, measures.
Sample pre-treatments: get about 5g potato chips sample and be placed in mortar and grind, the acrylamide standard items of different quality are added in sample, then sample is transferred in 50mL centrifuge tube, add the grease removal of 10mL normal hexane, Nitrogen evaporator dries up, then add 20mL ultrapure water ultrasonic extraction 15min, filter for subsequent use with the water system filtering membrane of 0.22 μm.
Experimental result is in table 1, and potato chips recovery Assay 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. the method for the detection of the collosol and gel molecular imprinting electrochemical sensor based on a nano material compound acrylamide, it is characterized in that: the method to be modified with carbon nano-tube, the glass-carbon electrode of the compound of golden nanometer particle and shitosan, the sol gel solution be placed in containing acrylamide carries out electrochemical deposition, obtained molecular imprinting electrochemical sensor, with this sensor, the acrylamide in sample is directly detected, wherein, containing adopting 3-aminopropyl trimethoxysilane as function monomer in the sol gel solution of acrylamide, tetraethoxysilane is as crosslinking chemical.
2. as claimed in claim 1 based on the method for the collosol and gel molecular imprinting electrochemical sensor detection acrylamide of nano material compound, it is characterized in that: described compound be by activation after carbon nano-tube sulfhydrylation, make its surface with sulfydryl, use ultrapure water again, at room temperature after drying, the carbon nano-tube of sulfydryl is with to add the ratio of 1ml solution of gold nanoparticles in 1mg, the carbon nano-tube of band sulfydryl is mixed 0.5-1.5h with solution of gold nanoparticles, obtains 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, obtained.
3. as claimed in claim 2 based on the method for the collosol and gel molecular imprinting electrochemical sensor detection acrylamide of nano material compound, it is characterized in that: described by activation after carbon nano-tube sulfhydrylation refer at room temperature, be first hatch 0.5-1.5h in the mixed liquor of 50mg/mLEDC and 50mg/mLNHS of 1:1 in volume ratio by the carbon nano-tube after activation, 0.5-1.5h is hatched again in cysteamine, wherein, the addition of mixed liquor is that the carbon nano-tube after every 1mg activates adds 1ml mixed liquor, half Guang by addition be every 1mg activate after carbon nano-tube add 1ml cysteamine.
4. as claimed in claim 3 based on the method for the collosol and gel molecular imprinting electrochemical sensor detection acrylamide of nano material compound, it is characterized in that: the activation of described carbon nano-tube is acid mixture ultrasonic process 3-4h carbon nano-tube being placed in the concentrated sulphuric acid that volume ratio is 3:1 and red fuming nitric acid (RFNA), by extremely neutral for the carbon nano-tube solution ultrapure water centrifugal elutriation obtained, obtain carboxylated carbon nano-tube, wherein, the addition of acid mixture is that every 25mg carbon nano-tube adds 4ml acid mixture.
5., as claimed in claim 4 based on the method for the collosol and gel molecular imprinting electrochemical sensor detection acrylamide of nano material compound, it is characterized in that, described centrifugal rotational speed is 9000-11000r/min, and the time is 4-6min.
6., as claimed in claim 2 based on the method for the collosol and gel molecular imprinting electrochemical sensor detection acrylamide of nano material compound, it is characterized in that, described golden nanoparticle solution refers to by 1ml 1%HAuCl
4solution adds the ratio of 99ml ultrapure water, by HAuCl
4solution and ultrapure water mixing, at 150-250r/min, at 220 DEG C, after magnetic stirring apparatus is heated to boiling, then press 100ml0.01%HAuCl
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 stirs 8-12min, be cooled to room temperature after solution is by grey to bright redness.
7. as claimed in claim 1 based on the method for the collosol and gel molecular imprinting electrochemical sensor detection acrylamide of nano material compound, it is characterized in that, the described sol gel solution containing acrylamide is the ratio adding 0.4g-0.6g acrylamide in the tetrahydrofuran solution of 4-5mL, acrylamide is joined in tetrahydrofuran solution and dissolves, the ratio adding 0.2mL function monomer 3-aminopropyl trimethoxysilane in 0.4g-0.6g acrylamide again in lysate adds 3-aminopropyl trimethoxysilane, 10-15min is stirred with 250-350r/min, the last ratio adding 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, 2h is stirred with 250-350r/min, obtain.
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| CN106432645B (en) * | 2016-09-26 | 2018-07-17 | 山东省分析测试中心 | A kind of " sulfydryl-gold " modified silica-gel surface Sudan molecules imprinted material, preparation method and application |
| CN109935378B (en) * | 2017-12-15 | 2021-07-30 | Tcl科技集团股份有限公司 | Composite nano-particles and preparation method and application thereof |
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